Multiflash For Windows

User Guide for
Multiflash for Windows

Infochem Computer Services Ltd
Version 3.3
5 Decemberr 2003

13 Swan Court
9 Tanner Street
London SE1 3LE
Tel: +44 [0]20 7357 0800
Fax: +44 [0]20 7407 3927
e-mail: info@infochemuk.com
This User Guide and the information contained within is the copyright of Infochem Computer Services Ltd.

13 Swan Court
9 Tanner Street
London SE1 3LE, UK
Tel:+44 [0]20 7357 0800
Fax:+44 [0]20 7407 3927
e-mail:info@infochemuk.com
Disclaimer
While every effort has been made to ensure that the information contained in this document is correct and that the
software and data to which it relates are free from errors, no guarantee is given or implied as to their correctness or
accuracy. Neither Infochem Computer Services Ltd nor any of its employees, contractors or agents shall be liable for
direct, indirect or consequential losses, damages, costs, expenses, claims or fee of any kind resulting from any
deficiency, defect or error in this document, the software or the data.
Contents
Overview 1
Introduction .................................................................................................................................. 1
Multiflash phase equilibrium utility.............................................................................. 1
Chemreact ...................................................................................................................... 2
Multiflash Software System......................................................................................................... 2
Documentation ............................................................................................................................. 2
Overview........................................................................................................................ 2
New Features and Changes in Version 3.3 ................................................................... 3
Running Multiflash........................................................................................................ 3
HELP.............................................................................................................................. 4
Case studies ................................................................................................................... 4
Appendix - Multiflash Commands................................................................................ 4
Installation .................................................................................................................................... 4
New Features and Changes in Version 3.3 7

Introduction .................................................................................................................................. 7
Models .......................................................................................................................................... 7
PC-SAFT ....................................................................................................................... 7
Regular Solution ............................................................................................................ 7
Flory-Huggins................................................................................................................ 7
Dortmund Modified UNIFAC....................................................................................... 8
Diffusivity...................................................................................................................... 8
Penneloux density correction ........................................................................................ 8
BIPs .............................................................................................................................................. 8
Fluid characterisation ................................................................................................................... 8
Black Oil Analysis......................................................................................................... 8
Supplementary information........................................................................................... 8
Plotting........................................................................................................................... 8
Matching....................................................................................................................................... 9
Asphaltene .................................................................................................................................... 9
Databanks ..................................................................................................................................... 9
Properties ....................................................................................................................... 9
Components ................................................................................................................... 9
Fitting pure component properties ................................................................................ 9
Phase envelope plotting.............................................................................................................. 10
Units............................................................................................................................................ 10
Cut and paste .............................................................................................................................. 10
Tables.......................................................................................................................................... 10
Interfaces .................................................................................................................................... 10
Simple Tutorial 11
Introduction ................................................................................................................................ 11
Starting Multiflash...................................................................................................................... 11
Defining a problem in Multiflash .............................................................................................. 12
Problem setup file........................................................................................................ 12
Loading an existing problem file ............................................................................................... 12
Loading a problem setup file....................................................................................... 13
The results.................................................................................................................... 13
User Guide for Multiflash for Windows Contents iii

Additional calculations................................................................................................ 14
Setting up a problem interactively ............................................................................................. 15
Clearing previous problems......................................................................................... 15
Defining the model ...................................................................................................... 16
Defining the components............................................................................................. 16
Define Input Conditions .............................................................................................. 17
Carrying out the flash calculation ............................................................................... 17
Additional calculations................................................................................................ 18
Phase envelope............................................................................................................. 18
Saving a problem setup .............................................................................................................. 19
Printing the output...................................................................................................................... 20
Saving the output........................................................................................................................ 20
Starting a new problem .............................................................................................................. 21
How to exit the program ............................................................................................................ 21
Input 23
Introduction ................................................................................................................................ 23
Input files.................................................................................................................................... 23
Menu options.............................................................................................................................. 24
File ............................................................................................................................... 24
Edit ............................................................................................................................... 24
Select............................................................................................................................ 25
Tools ............................................................................................................................ 25
Calculate ...................................................................................................................... 25
Table ............................................................................................................................ 26
Help.............................................................................................................................. 26
Toolbar buttons .......................................................................................................................... 26
Dialogue boxes, text boxes, tab controls, drop-down tables and menus .................................. 26
Commands.................................................................................................................................. 27
Models 29
Introduction ................................................................................................................................ 29
What is a model? ........................................................................................................................ 29
What types of model are available?........................................................................................... 29
Equation of state method ............................................................................................. 30
When to use equation of state methods....................................................................... 30
Equations of state provided in Multiflash ................................................................... 30
Activity coefficient methods ....................................................................................... 34
Activity coefficient equations in Multiflash ............................................................... 35
Gas phase models for activity coefficient methods .................................................... 36
When to use activity coefficient models ..................................................................... 36
Models for solid phases ............................................................................................... 36
Other thermodynamic models ..................................................................................... 42
Transport property models .......................................................................................... 42
How to specify models in Multiflash......................................................................................... 44
How to load a model.................................................................................................... 44
What the model definition means................................................................................ 46
How to change a model ............................................................................................... 47
Loading hydrate models .............................................................................................. 47
The Freeze-out model.................................................................................................. 48
How to define a wax model......................................................................................... 49
How to define the asphaltene model ........................................................................... 50
Combined Solids Model .............................................................................................. 50
Troubleshooting - models .......................................................................................................... 51
Incorrect path ............................................................................................................... 51
Model is not licensed................................................................................................... 52
Groups not available for UNIFAC model................................................................... 52
Binary interaction parameters .................................................................................................... 53
Number of BIPs related to any model......................................................................... 53
iv Contents User Guide for Multiflash for Windows

Units for BIPs .............................................................................................................. 53
Temperature dependence of BIPs ............................................................................... 54
BIPs available in Multiflash ........................................................................................ 54
Viewing BIP values ..................................................................................................... 54
Supplementing or overwriting BIPs............................................................................ 56
Troubleshooting - BIPs .............................................................................................................. 58
Units............................................................................................................................. 58
Order of components ................................................................................................... 58
Number of BIPs for the model .................................................................................... 58
Naming the components .............................................................................................. 59
BIP databank................................................................................................................ 59
BIPs not displayed ....................................................................................................... 59
Components 61
Introduction ................................................................................................................................ 61
Normal components..................................................................................................... 61
Condensed components ............................................................................................... 63
Petroleum fractions...................................................................................................... 63
Defining a mixture (stream) in Multiflash................................................................................. 64
Specifying the data source........................................................................................... 64
Selecting components.................................................................................................. 65
Adding, inserting, replacing and deleting components .............................................. 68
Viewing and editing pure component data. ................................................................ 69
User-defined components .......................................................................................................... 71
Stream types ............................................................................................................................... 76
Hydrate inhibitors....................................................................................................................... 79
Inhibitor calculator ...................................................................................................... 79
Salt calculator .............................................................................................................. 81
Troubleshooting - components .................................................................................................. 83
Databank not found ..................................................................................................... 83
Databank not licensed.................................................................................................. 84
Component cannot be found........................................................................................ 84
Too many components in the mixture......................................................................... 85
Petroleum fractions 87
Introduction ................................................................................................................................ 87
Defining petroleum fractions ..................................................................................................... 87
PVT Analysis ............................................................................................................................. 88
Analysis method .......................................................................................................... 89
Component list............................................................................................................. 89
Fluid composition ........................................................................................................ 92
Wax Content ................................................................................................................ 95
Water cut...................................................................................................................... 96
Total amount of fluid................................................................................................... 96
SARA Analysis............................................................................................................ 96
Characterisation ........................................................................................................... 96
Saving a PVT Analysis................................................................................................ 99
Troubleshooting PVT Analysis .............................................................................................. 99
Sensitivity to characterisation ..................................................................................... 99
Presence of water......................................................................................................... 99
Calculating petroleum fraction properties ................................................................................. 99
Editing petroleum fraction data................................................................................. 101
Matching using petroleum fraction properties......................................................................... 102
Matching dew and bubble points .............................................................................. 102
Matching wax appearance temperature..................................................................... 105
Matching liquid viscosity .......................................................................................... 106
Problems defining a petroleum fraction.................................................................... 108
Problems when matching .......................................................................................... 109
User Guide for Multiflash for Windows Contents v

Input conditions 111
Introduction .............................................................................................................................. 111
Specifying compositions .......................................................................................................... 111
Specifying temperature, pressure and volume......................................................................... 112
Specifying enthalpy, entropy and internal energy................................................................... 113
Troubleshooting - input conditions.......................................................................................... 113
Calculations (flashes) 115

Introduction .............................................................................................................................. 115
The basis of a flash calculation................................................................................................ 115
Flashes available in Multiflash ................................................................................................ 116
Isothermal (P,T) flash................................................................................................ 117
Isenthalpic flashes...................................................................................................... 117
Isentropic flashes ....................................................................................................... 117
Isochoric flashes ........................................................................................................ 118
Bubble and dew point flashes.................................................................................... 118
Fixed phase fraction flashes ...................................................................................... 118
Tolerance calculations ............................................................................................... 122
Provide a starting estimate ........................................................................................ 124
Phase diagrams .......................................................................................................... 124
Property output in Multiflash................................................................................................... 130
Troubleshooting - flash calculations........................................................................................ 131
Plot the phase envelope ............................................................................................. 132
Use the P,T flash........................................................................................................ 132
Limit the number of phases ....................................................................................... 132
Consider all types of solution.................................................................................... 133
Provide a starting estimate ........................................................................................ 133
Provide a key component .......................................................................................... 133
Chemical reaction..................................................................................................................... 133
Troubleshooting - chemical reaction ....................................................................................... 134
Units 135
Introduction .............................................................................................................................. 135
Working units ........................................................................................................................... 135
Default units ............................................................................................................................. 135
Changing units.......................................................................................................................... 135
Changing units interactively...................................................................................... 136
Changing units in a problem setup file ..................................................................... 136
Changing the default input and output units ............................................................. 137
Troubleshooting - units ............................................................................................................ 137
Output 139
Introduction .............................................................................................................................. 139
The results window. ................................................................................................................. 139
Font........................................................................................................................................... 140
Writing the results to a file....................................................................................................... 140
Printing the output.................................................................................................................... 141
Calculation output .................................................................................................................... 142
Output to Excel .......................................................................................................... 144
Phase envelope output.............................................................................................................. 144
Errors and warning messages................................................................................................... 144
Displaying status for current settings....................................................................................... 145
Troubleshooting - output.......................................................................................................... 146
The output does not include everything expected .................................................... 146
Phase labelling ........................................................................................................... 146
Phase envelope........................................................................................................... 146
Fonts........................................................................................................................... 146
vi Contents User Guide for Multiflash for Windows

Interfaces with other programs 147
Introduction .............................................................................................................................. 147
Pipesim PVT files..................................................................................................................... 147
OLGA ....................................................................................................................................... 148
CAPE-OPEN Interface............................................................................................................. 150
Help 151
Introduction .............................................................................................................................. 151
User Guide................................................................................................................................ 151
On-line help.............................................................................................................................. 151
Website support........................................................................................................................ 154
Technical support ..................................................................................................................... 154
Case studies - Pure component data 155

Introduction .............................................................................................................................. 155
Physical properties of a pure component................................................................................. 155
Defining the problem interactively ........................................................................... 155
Producing a problem setup file.................................................................................. 158
Obtaining properties from Pure component Data option.......................................... 159
Excel interface ........................................................................................................... 161
Case studies - Phase equilibria 163

Introduction .............................................................................................................................. 163
Oil and gas systems .................................................................................................................. 163
Calculating the bubble point curve ........................................................................... 164
Calculating the dew point curve................................................................................ 165
Phase envelope........................................................................................................... 166
Adding water to the system ....................................................................................... 167
Including a petroleum fraction .................................................................................. 168
Other flash calculations ............................................................................................. 169
PVT Analysis ........................................................................................................................... 171
Black Oil Analysis ................................................................................................................... 176
Refrigerant mixtures................................................................................................................. 177
Polar systems............................................................................................................................ 179
Modelling a polar mixture. ........................................................................................ 179
Liquid-liquid equilibria ............................................................................................. 182
Vapour-liquid-liquid equilibria ................................................................................. 183
Azeotropes ................................................................................................................. 183
Eutectics..................................................................................................................... 184
Polymers ................................................................................................................................... 185
Data input................................................................................................................... 185
Case studies - Hydrate dissociation, formation and inhibition 189

Introduction .............................................................................................................................. 189
Defining the hydrate models .................................................................................................... 189
Fluid phase model...................................................................................................... 190
Hydrate model ........................................................................................................... 190
Nucleation model....................................................................................................... 190
Ice model.................................................................................................................... 190
Phases......................................................................................................................... 190
Hydrate calculations with Multiflash....................................................................................... 191
Will hydrates form at given P and T ? ...................................................................... 192
Hydrate formation and dissociation temperature at given pressure ......................... 193
Hydrate formation and dissociation pressure at given temperature ......................... 195
Hydrate phase boundary ............................................................................................ 196
Other flash calculations with hydrates ...................................................................... 196
User Guide for Multiflash for Windows Contents vii

Maximum water content allowable before hydrate dissociation.............................. 196
Calculations with inhibitors ..................................................................................................... 197
Can hydrates form at given P and T ? ....................................................................... 198
Hydrate dissociation temperature at a given pressure .............................................. 199
Hydrate dissociation pressure at a given temperature .............................................. 199
Hydrate phase boundary ............................................................................................ 199
Amount of inhibitor required to suppress hydrates .................................................. 200
Salt inhibition............................................................................................................. 201
CPA model ............................................................................................................................... 203
Case studies Wax deposition 205

Introduction .............................................................................................................................. 205
Defining the wax model........................................................................................................... 205
Multisolid model........................................................................................................ 205
Coutinho wax model.................................................................................................. 206
Calculating wax appearance temperature (WAT) ................................................................... 206
Calculating wax precipitation .................................................................................................. 210
Case studies Asphaltene flocculation 211

Introduction .............................................................................................................................. 211
Input data .................................................................................................................................. 211
Defining the asphaltene model................................................................................................. 212
Calculating asphaltene flocculation conditions ....................................................................... 215
Sensitivity of calculations to variation in input data ............................................................... 219
Choice of Analysis method ....................................................................................... 219
Data Availability........................................................................................................ 220
No reservoir or flocculation conditions..................................................................... 222
Gas injection............................................................................................................................. 224
Titration .................................................................................................................................... 224
Case studies Combined solids 229

Introduction .............................................................................................................................. 229
Asphaltene flocculation............................................................................................................ 229
Wax and Asphaltene precipitation........................................................................................... 230
Hydrates, Waxes and Asphaltenes........................................................................................... 231
Case studies Excel spreadsheets 235

Introduction .............................................................................................................................. 235
UNFACFIT.xls......................................................................................................................... 235
Notes .......................................................................................................................... 235
UNIFAC..................................................................................................................... 236
Activity model worksheets........................................................................................ 236
VLEFIT.xls............................................................................................................................... 237
Solids.xls, Solids31.xls and Solids32.xls ................................................................................ 237
PVT Analysis............................................................................................................. 238
Match bubble point.................................................................................................... 238
Wax ............................................................................................................................ 239
Asphaltenes................................................................................................................ 240
Asphaltene with gas injection.................................................................................... 240
Hydrates ..................................................................................................................... 241
Case studies - chemical equilibria 243

Introduction .............................................................................................................................. 243
Xylene isomerisation................................................................................................................ 243
Steam cracking of ethane ......................................................................................................... 244
viii Contents User Guide for Multiflash for Windows

Appendix - Multiflash Commands 247
Introduction .............................................................................................................................. 247
When you may need to use commands.................................................................................... 247
Defining models ....................................................................................................................... 247
Supplying an external file of BIPs........................................................................................... 248
Defining phase descriptors and key components .................................................................... 248
Index 253
User Guide for Multiflash for Windows Contents ix

Overview
Introduction
Multiflash is an advanced software package for performing complex equilibrium
calculations quickly and reliably. The main utility is a multiple phase
equilibrium algorithm that is interfaced to Infochems package of
thermodynamic models and a number of physical property data banks.
The program also contains Infochems Chemreact utility for performing
simultaneous phase and chemical equilibrium calculations.
Multiflash phase equilibrium utility

Multiflash can perform multiphase equilibrium calculations between any number
of phases of different types. Each property of each phase may be described by a
different thermodynamic model if required. The phases that can be modelled
include gases, liquids and solids, including hydrates, waxes and asphaltenes,
depending on which models are available under your licence.
Multiflash incorporates a phase stability analysis procedure whereby it can
establish automatically which of the possible phases are present at equilibrium.
Phase equilibria can be calculated for the following conditions:
fixed pressure and temperature
fixed fraction of any specified phase at fixed pressure (includes
dew and bubble points)
fixed fraction of any specified phase at fixed temperature (includes
dew and bubble points)
fixed pressure and enthalpy
fixed temperature and enthalpy
fixed pressure and entropy
fixed temperature and entropy
fixed pressure and internal energy
fixed temperature and internal energy
fixed pressure and volume
fixed temperature and volume
fixed internal energy and volume
User Guide for Multiflash for Windows Overview 1

fixed entropy and volume
fixed enthalpy and entropy
fixed pressure, temperature and fraction of any specified phase
(variable composition)
A full range of thermodynamic and transport properties is available for any fluid
phase.
Chemreact
Chemreact is a utility for performing simultaneous phase and chemical
equilibrium calculations. Currently Chemreact can handle equilibria involving
combinations of one gas phase, one liquid phase and any number of pure solids.
It is interfaced to the same package of thermodynamic models and physical
property data banks as the phase equilibrium utility.
As in the phase equilibrium utility, Chemreact incorporates a phase stability
analysis procedure to establish automatically which phases are present at
equilibrium.
Chemreact can calculate equilibria for the following specifications:
fixed pressure and temperature
dew point at fixed pressure
dew point at fixed temperature
bubble point at fixed pressure
bubble point at fixed temperature
When using Chemreact the user does not need to specify any reaction
mechanism but only list all the possible products and reactants.
Multiflash Software System

In addition to the Microsoft Windows program Multiflash is also available as an
add-in for use with the Microsoft Excel spreadsheet program, for use with
Matlab, as a DLL and as a suite of sub-routines for interfacing to other
application packages. A CAPE-OPEN physical property package interface is
also available. The package can be accessed from programs written in Fortran,
Visual Basic, VBA and C. All versions share the capability to use the problem
setup files which can store all aspects of a users problem, see Setting up a
problem interactively on page 15.
Separate documentation is available for these interfaces.
Documentation
The supporting documentation is grouped into sections.
Overview
This section describes what the Multiflash software is used for, what it contains
and how it is made available.
2 Overview User Guide for Multiflash for Windows

New Features and Changes in Version 3.3
New developments and additions are listed, although the detailed review of how
to use new features will be covered in the appropriate section. Information is
also given on changes to code or data which may give rise to different results
from those obtained with earlier versions of Multiflash.
Running Multiflash
Each section provides details on different aspects of the software.
Simple tutorial
This section is based on starting the program and running a simple example with
step by step instructions.
Input
This section provides an overview of the various ways you can enter data and
commands in Multiflash for Windows.
Models
This section describes the mixture models available in Multiflash and shows how
to define a model. How and when to use models is reviewed, together with the
availability and use of model interaction parameters.
Components
The type of components that are available from Multiflash are defined, together
with a description of the physical property databanks available. This section also
shows how to search for and select components, including how to define and edit
data for petroleum fractions.
Petroleum Fractions
How to carry out PVT characterisation and calculate petroleum fraction physical
properties.
Input Conditions
The necessary conditions for carrying out different types of calculations are
defined, together with how to enter and change these within the program.
Calculations
The final step in running Multiflash, the specification of the calculations which
can be carried out, and the circumstances where they might be most appropriate,
are outlined.
Units
This section defines the standard working units of the software, the range of
options available for input and output units and how to change them.
Output
This section reviews the different levels of output available, where output is
reported and how it may be saved.

HELP
The various types of help available and how to access them are reviewed.
Case studies
Additional examples of how to tackle typical problems using Multiflash are
provided.
Appendix - Multiflash Commands

Nearly all the facilities available in the command processor version of Multiflash
have been incorporated as menu options in the current version of Multiflash for
Windows, and can be now readily accessed from either menu options or tool bar.
An example would be the ability to edit or change model binary interaction
parameters (BIP) in the BIP values window by selecting the BIPs option from
the Tools menu. However a Tools Command option is still available which
allows the user to enter any command and apply this in the Windows version.
Those commands which users of the Windows version of Multiflash may find
useful are discussed in the appropriate section of the User Guide or in the
Appendix.
Commands are used to create or edit problem setup files for use with Multiflash.
A Contents list and an Index are also supplied to help you find your way
around the User Guide.
Installation
Information on how to install Multiflash software is provided in the the separate
"Installation Guide for Multiflash for Windows".
4 Overview User Guide for Multiflash for Windows

New Features and Changes in
Version 3.3
Introduction
There are several improvements and extensions in Multiflash 3.3. The major
development is the inclusion of new models, particulalry PC-SAFT. One of the
major applications of PC-SAFT is the calculation of phase equilibria for polymer
systems, thus extending the industrail fields Multiflash can serve.
Changes have been made to improve the robustness of calculations, partly due to
difficulties in solution for polymer containing systems. In some cases you may
find that calculated results are vary slightly from previous versions.
Models
Descriptions and references detailing the models are provided in our "Models
and Physical Property Guide"
PC-SAFT
PC-SAFT stands for the Perturbed Chain Statistical Associating Fluid Theory
and it incorporates current ideas of how to model accurately the detailed
thermodynamics of fluids within the framework an equation of state.
It is a development of the SAFT model that has been shown to give good results
for a wide range of polar and non-polar substances including polymers. The
model appears to be one of the most accurate and realistic equations of state
currently available for modelling polymer systems.
Regular Solution
Regular solution theory can be used for vapour-liquid calculations for mixtures
of non-polar or slightly polar components. The theory is applicable to systems
which exhibit negligible entropies and volumes of mixing. However, it has been
largely superseded by equations of state
Flory-Huggins
Flory-Huggins theory is able to describe systems which include some long chain
molecules. It has consequently applied to model polymer systems but it has been
largely superseded by other models such as PC-SAFT.
User Guide for Multiflash for Windows New Features and Changes in Version 3.3 7
Dortmund Modified UNIFAC
The Dortmund modified UNIFAC is a variant of UNIFAC that is better able to
represent the simultaneous vapour-liquid equilibria, liquid-liquid equilibria and
excess enthalpies of polar mixtures. Like original UNIFAC, however, it does not
allow for the presence of light gases in the mixture.
Diffusivity
Multiflash now returns effective diffusion coefficients for a liquid of defined
composition. Gas diffusion coefficients are calculated using Fuller's method,
liquid diffusion using the Hayduk-Minhas method.
Penneloux density correction

This correlation has been used in previous versions of Multiflash to match the
density calculated from the equation of state to that stored in the chosen physical
property data system. For liquid components the volume shift is now treated as a
linear function of temperature; the density is matched at 290.7K and 315.7K so
as to reproduce the density and thermal expansivity of liquids over a range of
temperatures centred on ambient.
BIPs
The INFOBIPS databank has been expanded to include interaction parameters
for Wilson E, UNIQUAC and NRTL for mixtures containing aldehydes, ethers
and ketones.
Fluid characterisation
Black Oil Analysis

The PVT Analysis facility has been extended to allow for Blackoil input. This is
based on a minimum specification of a condensate or oil, often the only data
available at the early stages of a project. The absolute minimum information
required is the gas gravity, the stock tank oil specific gravity ad the Solution
GOR (also known as Rs). If data is available additional information such as the
Watson-K factor and the gas analysis can also be supplied. From this minimum
information Multiflash can be used to create a compositional analysis for the
fluid with the user specifying the starting carbon number cut and the number of
pseudocomponents.
Supplementary information
The PVT Anaysis forms have been revised to clarify the required input
information for molecular weight and specific gravity.
Plotting
Also new in Multiflash 3.3 is a display that shows the plot of the experimental
compositional data compared to the fitted distribution.
8 New Features and Changes in Version 3.3 User Guide for Multiflash for Windows
Matching
The Matching facilities for bubble and dew points and liquid viscosity also
include a display of the experimental and matched data. The numeric values for
the matched data are also automatically displayed in the results window.
Asphaltene
The procedure for generating the asphaltene model parameters from titration data
has now been automated and included in the Matching Asphaltene Phase facility.
Databanks
The Infodata and DIPPR databanks have been restructured. This may not be
apparent to the user but will allow future versions to store efficientlly new
properties required by the introduction of new models.
Properties
The pure component record has been extended to include the pure component
SAFT parameters required by the PC-SAFT model. Actual values have been
supplied for typical solvents, values for polymers have to be entered as part of
the user defined data.
The Dielectric constant has been added as a temperature dependent property.
Again supplied values are limited to water, methonal and glycols, but the user
can of course provide supplemental data if necessary.
Components
Six new components have been aded to Infodata. These are
SF6
and the amines
MDEA
MEA
DEA
TEA
Piperazine
Data for some other components have been revised.
Fitting pure component properties

The equations used for fitting pure component property data ae only referredto
by number as part of the displayed data record. The detailed description has, and
still is, available from the "Programmers Guide" or the "Command Refrence
Manual". For conveneience we have also included this information in the
"Models and Physical Property Guide".
Spreadsheets to for pure component data to the stored equations have been
implemented. They will be supplied to Multiflash licensees on request.
User Guide for Multiflash for Windows New Features and Changes in Version 3.3 9
Phase envelope plotting
The tracing of the phase boundaries has been improved to handle the ever more
complex phase behaviour predictions.
The allocation of a different colour to each new phase line has been automated to
clarify the phase envelpe plots.
Units
A choice of units has been provided for Surface Tension, and a tab for this
property has been added to the Units definition menu. A new tab has also been
introduced for diffusion coefficients.
The deafult set of units is SI. For the convenience of user we have also
introduced a global unit change to "All metric" or "All British". These units set
are described in more detail in Changing units on page 135.
Cut and paste

Users have alwys been able to cut and paste results from the main Multiflash
Window to other windows programs, such as Word. The display of the
calculated results has also been re-formatted so that thay can be copied directly
into Excel and the columns recognised and delineated. The table input for
composition and PVT Analysis have also been modifed so that they can accept
input direct from Excel, making interchange of data easier and less prone to eror.
Tables
Multiflash can be used to provide tabluar input for other application packages.
Of the commercially available programs supported in this way PIPESIM and
OLGA remain but HTFS has been removed. The table requirement has been
superseded. The existing tabular output has ben upgraded.
Interfaces
The CAPE-OPEN interface has been upgraded to version 1.0. The
Matlab/Simulink interface is also upgraded with each new Multiflash release.
10 New Features and Changes in Version 3.3 User Guide for Multiflash for Windows
Simple Tutorial
Introduction
This section concentrates on how to run Multiflash using a simple problem as an
example. The assumption is that the user is already familiar with Windows
terms and techniques.
Starting Multiflash
You start Multiflash by clicking on the MFW32 shortcut.
The Multiflash Main Window should then appear.
User Guide for Multiflash for Windows Simple Tutorial 11

If, in a previous run of Multiflash, an error has caused an abnormal termination,
you may see a message box saying Multiflash DLL already loaded. In this case
you may need to click the Start button and select restart the computer.
Defining a problem in Multiflash

You need, first of all, to define the problem you want to solve using Multiflash.
This means choosing the model you wish to use to describe your system, setting
the source for the pure component data, the components in the system and their
compositions, the input conditions (e.g. temperature and pressure) and the
calculation you wish to carry out. This is described in detail in the appropriate
section. Initially a simple problem as defined Multiflash is used to calculate the
physical properties of the system.
The system is 0.4 moles of butane and 0.6 moles of pentane. The model used to
describe the system is the Peng-Robinson equation of state with the pure
component data taken from the INFODATA databank and interaction parameters
from the default BIP databank called OILANDGAS. First we are going to
calculate the bubble point (the point at which the gas phase first appears) at fixed
pressure followed by an isenthalpic flash (a flash calculation at fixed enthalpy
and, in this case, pressure).
There are two ways of setting up the problem. You can prepare a problem
setup file using a text editor, either by typing in all the necessary commands or
by copying and editing an existing file. However, it is more usual to set up the
problem completely within Multiflash for Windows and save the problem file for
future use.This is activated by Save Problem setup from the File menu Save
Problem setup will save the current problem definition, excluding flash
calculation options.
Problem setup file

Infochem supplies a series of sample problem setup files covering typical
problem types. These can be used as examples when testing the program or can
be copied and edited to define your own problems. By convention problem
setup files for Multiflash have the extension .mfl.
Loading an existing problem file

Infochem has provided several problem set up files (extension .mfl) covering a
variety of typical problems. Any of these may be used as an example when
running Multiflash; the setup file used for the simple tutorial is C4C5.mfl.
If the problem set up file has been edited to include a full definition of the
problem, including input conditions and a specification of the flash calculation,
then once the file is loaded the flash calculation will be carried out and the
results shown. If it contains only a partial definition of the problem then the
remaining specifications must be completed interactively.
12 Simple Tutorial User Guide for Multiflash for Windows

Loading a problem setup file
The problem setup file for our tutorial is C4C5.mfl. This is loaded by
1. Either selecting File from menu bar, then selecting Load
Problem Setup from the sub-menu
or
Clicking on Load problem setup button .
This will activate the Load Multiflash File Dialogue box,
which will show a list of available setup files (*.mfl) contained in

the current directory.
2. Scroll to C4C5.mfl, which will now be highlighted, and either

double click on it or select it and click on OK. The Dialogue
box will disappear and the file will be read in. This file contains
the complete definition of the problem including:
Data sources
Model
Phase descriptors
Compounds
Compositions
Input conditions
Calculation
The results
The results of any calculations are displayed in the results section of the main
Multiflash window and the last set of input conditions echoed in the input
conditions section of the window. You can scroll up and down to look at earlier
calculations.The input conditions section of the main window will now look like
this

displaying the set pressure and the enthalpy for the final calculation, which was
an isenthalpic flash.
The results of the isenthalpic flash calculation will be the last item displayed the
results window
You can scroll up to look at the earlier bubble point calculation at a pressure of
10e5Pa.
Additional calculations
You can pre-set all the calculations you wish to carry out for any one problem
within the problem setup file. However, it is probable that once you have seen
the results of one calculation you may wish to make other changes or perform
other calculations.
Any of the input conditions may be changed by entering new values to overwrite
or supplement those shown in the input section of the main window. Simply type
the value for the input condition in the appropriate text box, ensure that all
necessary input conditions are defined for the flash calculation you wish to carry
out and then click on the appropriate flash icon or select the required flash from
the menu options.
Compositions for a mixture may be altered by clicking on the composition
button and editing the right-hand column of the drop-down table where the
amounts of each component are defined.
To replace a component or to add new components see Adding, inserting,
replacing and deleting componentsSome simple changes are shown below:
Change the pressure

1. Place cursor in Pressure box of the Conditions panel in the main
window and change the pressure to 20e5 Pa.
2. Click on P,H flash button

or
use the drop down menu by selecting Calculate in the menu bar,

then selecting Standard flashes in sub-menu and finally
selecting P,H flash in sub-sub-menu.
Change the enthalpy

1. Change the enthalpy for the isenthalpic flash by typing -1000 in
the enthalpy box of the Conditions section
2. Recalculate the isenthalpic flash by repeating step 2 as above.
Change the composition

1. Click on the Composition button in the Conditions section of the
main window. The component names are displayed in the first
column and the number of moles of each component in the mixture
is shown in the second column. Edit the mol column of the
drop-down table so that there are 3 moles of butane and 7 moles of
pentane.
2. Recalculate the isenthalpic flash as above
Carry out an isothermal flash

1. Enter a temperature in K in the temperature text box in the
Conditions section, e.g. 300K
2. Click on the P,T flash button

or
select the P,T flash option starting from Calculate in the Menu
bar.
Setting up a problem interactively

You can define all the necessary input for a problem calculation interactively.
This input must include:
Data sources
Model
Compounds
Compositions
Input conditions
Flash Calculation
Clearing previous problems

Each time you start Multiflash from the Windows icon you start with a clean
sheet, i.e. there are no models or components pre-loaded. However, the
INFODATA databank, see Normal components on page 61, will be set as the
default data source. If you have already carried out a series of calculations for a
previous problem and want to start a new one then
Select Clear Problem Setup from the File menu.
This will remove the current specification and reset the unit definitions to those
in place when you started the program. INFODATA will still remain as the
default data source for the pure component data.

Defining the model
To define the model Select Select in the menu bar and from the drop-down
menu select Model set. A tabbed dialogue box will offer a choice of different
types of model, e.g. equation of state, activity coefficient method, hydrate, wax
and asphaltene or a combination of solid models. Within each group a specific
model along with a number of phases may be chosen by name and a combination
of transport models chosen. For general advice on which models to choose for
an application and a detailed definition of each model, see models.
Once you have selected a model a message will be displayed to
tell you that the model has been successfully loaded, click on OK
and close the Select Model dialogue box to return to the main
window. The model set will include a data source for binary
interaction parametersWe will use the Peng-Robinson equation of state, see
Peng-Robinson equation of state on page 30, for this problem. Select Select in
the menu bar and from the drop-down menu select Model set to open the Select
Model Set tabbed dialogue box. In the Model Set window, select Equations of
State, and from the following menu select PR. You can also select phases and
transport property models in this window but the default set will already be
selected. After the selection, click the Define Model button. You should see the
following message.
Click on OK to return to the Select Models dialogue box. Click on Close to

return to the main window.
Defining the components

Choose the components for any problem by Selecting Select then selecting
Components from the sub-menu. Alternatively you can click on the Select
Components button, . Either will result in the display of the Select
Components Dialogue box.
Specify the data source and the individual components. Components may be
selected in a variety of ways e.g. by name, by scrolling through a list or by
searching for a formula. The various methods are fully described in Selecting
components on page 65.
Choose the components needed for the problem, in this case butane and pentane,
by:
1. Selecting Select again, but this time selecting Components
from the sub-menu. Alternatively you can click on the Select
Components button, . Either will result in the display of the
Select Components Dialogue box. At this stage we will ignore the
search facilities and enter the components by simplest route
possible.
2. INFODATA will be the default data source. Make sure the Name
option button is selected.
3. Type
butane

in the Enter Name box and either press Enter
or click on the Add button to transfer butane to the Components
selected list. Do the same for pentane.
4. Click on the Close button, this will return you to the Main
Window.
5. To check the components are correctly loaded, click on the
Composition button and check the drop-down table, which should
look like this
Define Input Conditions

Before a flash calculation can be carried out you must define all necessary input
conditions, including the composition of the mixture. All input conditions are
specified in the input condition section of the main window.
The composition is entered by clicking on the Composition button. The drop-
down table shows the chosen components in the left-hand column and the
amount of each component in the mixture is typed in the right-hand column.
The default unit for amounts is moles.
Other input conditions will depend on the type of flash calculation to be carried
out, e.g. for an isothermal flash you must type in a pressure and a temperature
in the appropriate text boxes and in the units shown next to themEnter the input
conditions in the Conditions section of the main window
Compositions
1. Type the number of moles of each component, in this case 0.4 for
butane and 0.6 for pentane.
2. Close by clicking on roll-up button if you wish. The table can
remain down if you prefer.
Pressure
Type the pressure in Pa., in this case 10e5, in the Pressure text box.
Carrying out the flash calculation

To carry out a flash calculation you either click on the appropriate flash button
or select the required flash from the menu.
Only the most commonly encountered flash options have been allocated buttons;
these are the isothermal flash, dew and bubble points, isenthalpic and isentropic
flashes at fixed pressure and fixed phase flashes. To carry out the latter you also
have to fill in supplementary information in a dialogue box.
Other flashes, such as isochoric flashes or isentropic and isenthalpic flashes at
fixed temperature, are specified using the options accessed under Calculate in the
menu barTo calculate the bubble point at fixed pressure, either
Click on the bubble point at fixed pressure button,

or
1. Select Calculate from the menu bar, then
2. Select Bubble or dew point flashes in sub-menu, then
3. Select P, Bubble point flash in the next menu.
To carry out the isenthalpic flash, type -11078 in the enthalpy text box and
click on the P,H button. The results will be identical to those shown earlier.
Additional calculations
Any of the input conditions may be changed by entering new values to overwrite
or supplement those shown in the input section of the main window. Simply type
the value for the input condition in the appropriate text box, ensure that all
necessary input conditions are defined for the flash calculation you wish to carry
out and then click on the appropriate flash icon or select the required flash from
the menu options.
Compositions for a mixture may be altered by clicking on the composition
button and editing the right-hand column of the drop-down table where the
amounts of each component are defined.
To replace a component or to add new components see Adding, inserting,
replacing and deleting components.
Phase envelope
You can also plot the complete phase envelope by
1. Clicking on the phase envelope button or clicking on the

Calculate menu followed by clicking on Phase Envelope
2. In the Phase Envelope tabbed dialogue box click on VLE Autoplot
The phase envelope will be displayed in a separate window.

The phase diagram may be edited or printed as described elsewhere,
Customising the phase envelope plot on page 145. Alternatively it can be
exported to Excel, provided you are running Excel 97, 2000 or XP.
Saving a problem setup

Once you have defined the model, components, compositions and conditions
interactively you can create a problem setup file containing this information for
future use. It does not matter whether these were entered through dialogue
boxes, from an existing problem setup file or the Tools/Command option. To
save the setup either
Select File from the menu bar and then select Save Problem Setup
or
Click on Save problem setup button,

The dialogue box that is activated allows you to specify the name of the .mfl file
and the directory where you want it stored.
Multiflash will provide a default file name which can be overwritten.

Printing the output
You can print the output from your calculations by
Selecting File from the menu bar, then
selecting Print Results
or
Clicking on the Print results button,

This leads you to a print panel (see below), so that you can change the printers
setting and its properties, and print out all the output currently stored in the
results window.
If you only wish to print part of the output you should select the relevant section
by highlighting it with the cursor. This time the print range in the print panel
shows you the option of printing out only the selected text.
Alternatively you can cut or copy the relevant sections and paste them to another
application, such as Word.
Saving the output

The output from Multiflash is described in detail elsewhere, see Output on
page 139 All the output from any run is automatically stored in a file called
MFLASH.LOG. This file will be overwritten when the program is started unless
you rename it. If you wish to save the output to another file directly from
Multiflash, then
Select File from the menu
Select Save Results
As with printing the results you will see a message box which allows you to
write the entire output window to file. If you have previously highlighted a
section of the output then the message box offers the option of writing the
selected text to file.
A dialogue box allows you to choose the file name and directory. The
convention is that the extension for output files is .out, but you may alter this if
you wish.

Note that the amount of output produced by any calculation or problem setup file
is limited to 32kb of text. Any output beyond this limit will not be displayed on
the screen or in the log file.
Starting a new problem

To load a new problem
Select File from the menu, followed by
Selecting Clear Problem Setup.
The message Clear current problem setup will appear in the results window.
Select a new problem setup file or enter a new problem interactively.
How to exit the program

To exit Multiflash
Select File from the menu bar then
Select Exit

Input
Introduction
This section concentrates on the methods of providing input information for
Multiflash, rather than the specification of that input information, which will be
discussed in the sections relating to the various types of information which must
be supplied.
The information you need to supply will include
Model specification
Data sources for pure component data
Compounds in the mixture.
Input conditions including composition
Calculation (flash) to be carried out
You may also wish to alter
Units
Level of property output
You can supply all of the input specification interactively, all of the input
specification in a problem setup file or use a mixture of both.
Input files
An input file may contain a full specification of the problem or define only part
of it.
We have usually referred to the former as problem setup files (extension .mfl)
and have supplied several to use as test examples or templates for producing
your own setup files. As a minimum they should define the model, data sources
for pure components and model interaction parameters (BIPs) and components
for your mixture. Usually they will also contain a composition and possibly the
flash calculation and the input conditions related to it.
We recommend that any setup file that contains the numerical values for any
input variables also defines the units for these to prevent any mismatch on
loading.
Typical of partial setup files are those which are supplied to define a model
(extension .mfc). These contain a specification of the model and a list of phase
descriptors, which give the possible phases that may be encountered in
calculations. The .mfc files we supply normally define up to four phases: one
User Guide for Multiflash for Windows Input 23

vapour phase, two liquid phases and a water phase. More phases are needed for
some applications, for example the hydrate I/II model configuration file contains
seven phase descriptors, the hydrate I/II/H model configuration file has eight
phase descriptors.
Exceptions are the input files for PVT analysis. They do not need to define
either a model or a source for the BIPs but must include a source for the pure
component data.
Menu options
Multiflash for Windows includes a menu bar and several drop-down menus.
These allow you to control all aspects of running Multiflash for Windows,
grouped under the main menu headings of File, Edit, Select, Tools, Calculate,
Table and Help.
File
The File menu controls the loading, saving, clearing and printing of setup files
and the saving and printing of results.
Where you need to define further items, such as the directory and file to be
loaded, a dialogue box will be activated.
If the setup files you want have been used recently, you may find them listed. To
load a setup file from the list, move the pointer to the file and double click on it.
Edit
This controls the normal windows editing functions of Cut, Copy and Paste,
which can be used on text in the results window.
24 Input User Guide for Multiflash for Windows

Select
The Select menu option allows you to select the components, freeze-out model
and related components, PVT Lab. Input, models, level of property output,
stream types, units and the use of starting values. All the menu options except
Use Starting Values activate dialogue boxes.
Tools
The Tools menu allows you to use commands to access all options that are
supported by Multiflash. This is most useful for options which have not yet
been allocated a button or specific menu item in Multiflash for Windows. The
Tools menu also allows you to view and edit the properties of any component in
the stream and any binary interaction parameters being used. The Inhibitor
calculator allows you to add water and inhibitors without defining them in the
pure component list. It also allows you to define the amount of the inhibitor in
the water phase in mass, mole or volume units and the calculator then determines
the amount of inhibitor to be added to the overall composition in the units
currently in use. The Salt Calculator is part of the Inhibitor Calculator dialog
box. The Matching function amends the properties of petroleum fractions in the
stream to reproduce user supplied liquid viscosity, wax appearance temperature
and dew or bubble points. For the asphaltene phase the matching function
modifies the asphaltene model parameters.
Calculate
The Calculate menu option controls the choice of standard flash options,
tolerance calculation, phase envelope and chemical equilibria. Sub-menus are
activated for Standard Flashes, Bubble and Dew Point Flashes and Chemical
Equilibria. Dialogue boxes are activated for Fixed Phase Fraction Flashes, (see
Fixed phase fraction flashes on page 118), tolerance calculation, (see
Tolerance calculations on page 122), and phase envelope, (see Phase
diagrams on page 124).

Table
The Table menu is for the option of creating output files for use with other
applications, currently PIPESIM and OLGA. See Interfaces with other
programs on page 147.
Help
The HELP menu enables you to get help on a variety of topics, see Help on
page 151.
Toolbar buttons
Some of the most common menu options have been allocated individual Toolbar
buttons.(located in the Tool bar section of the main window or in individual
dialogue boxes)
Dialogue boxes, text boxes, tab controls, drop-down

tables and menus
Where additional information is needed for any menu option then you may be
asked to supply this through dialogue boxes, text boxes, tab controls, drop-down
tables or menus. These are described individually in the sections relating to the
input variable being specified.
26 Input User Guide for Multiflash for Windows

Commands
There are some Multiflash facilities which have not been allocated a menu
option. These are still accessible by using the Tools Command menu option.
Some of these commands will be discussed in other sections where they are
used in examples or case studies. They can be specified in Multiflash either as
part of a problem setup file or through the Tools/Command menu, options, e.g.
will provide more details of the chosen model, including the name
of the associated BIP set.

Models
Introduction
This section defines what a model is in terms of the Multiflash nomenclature,
what models are available and when you might wish to use them, as well as the
practical means of specifying and using them in Multiflash. For information on
specifying models, see How to specify models in Multiflash on page 44.
Detailed model descriptions may be found in our separate "Models and Physical
Properties Guide".
What is a model?
Within the context of Multiflash, a model is a mathematical description of how
one or more thermodynamic or transport properties of a fluid or solid will
depend on pressure, temperature or composition.
What types of model are available?

The key thermodynamic property calculation carried out within Multiflash is the
determination of phase equilibrium. This is based on the fundamental
relationship that at equilibrium the fugacity of a component is equal in all
phases. For a simple vapour-liquid system
fiv = fil
v l
where f i is the fugacity of component i in the vapour phase and f i is the
fugacity of component i in the liquid phase.
The models used in Multiflash to represent the fugacities from the phase
equilibrium relationship in terms of measurable state variables (temperature,
pressure, enthalpy, entropy, volume and internal energy) fall into two groups,
equation of state methods and activity coefficient methods. The basis of each of
these methods is described below.
With an equation of state method all thermal properties for any fluid phase can
be derived from the equation of state. With an activity coefficient method the
vapour phase properties are derived from an equation of state, whereas the liquid
properties are determined from the summation of the pure component properties
to which a mixing term or an excess term has been added.
Multiflash may also be used to calculate the phase equilibrium of systems
containing solid phases, either mixed or pure. These may occur either when a
User Guide for Multiflash for Windows Models 29

normal fluid freezes or may be a particular solid phase such as a hydrate, wax or
asphaltene. Models used to represent these solids are discussed below.
The transport properties of a phase (viscosity, thermal conductivity and surface
tension) are derived from semi-empirical models which will be discussed later.
Equation of state method

An equation of state describes the pressure, volume and temperature (PVT)
behaviour of pure components and mixtures. Most equations of state have
different terms to represent the attractive and repulsive forces between
molecules. Any thermodynamic property, such as fugacity coefficients and
enthalpies, can be calculated from an equation of state relative to the ideal gas
properties of the same mixture at the same conditions.
When to use equation of state methods

Equations of state can be used over wide ranges of temperature and pressure,
including the subcritical and supercritical regions. They are frequently used for
ideal or slightly non-ideal systems such as those related to the oil and gas
industry where modelling of hydrocarbon systems, perhaps containing light
gases such as H2S, CO2 and N2, is the norm. Equation of state methods do not
necessarily represent highly non-ideal chemical systems, such as alcohol-water,
well. For this type of system, at low pressure, an activity coefficient approach is
preferable but at higher pressure you may need to use an equation of state with
excess Gibbs energy mixing rules, such as RKSA(Infochem).
All equations of state will describe any system more accurately when binary
interaction parameters (BIPs) have been derived from the regression of
experimental phase equilibrium data. BIPs are adjustable factors which are used
to alter the predictions from a model until these reproduce as closely as possible
the experimental data. The use of interaction parameters in Multiflash is
discussed separately, see Binary interaction parameters on page 53.
The thermal properties of any fluid phase can be derived from an equation of
state. However, one property which is often poorly represented by the simpler
equations of state is the liquid density. Multiflash offers enhanced versions of
both the Redlich-Kwong-Soave (RKS) and Peng-Robinson (PR) cubic equations
of state where the equation of state parameters can be fitted to reproduce both the
saturated vapour pressure using a databank correlation and the saturated liquid
density at 298K or Tr=0.7 (Peneloux method). These are referred to in
Multiflash as the advanced version of the particular equation of state.
Equations of state provided in Multiflash

The following equations of state are available in Multiflash.
Ideal gas equation of state

This model is normally used in conjunction with an activity coefficient method
when the latter is used to model the liquid phase. It could also be used to
describe the behaviour of gases at low pressure.
Peng-Robinson equation of state)

The Peng-Robinson (PRequation is a cubic equation of state.
30 Models User Guide for Multiflash for Windows

Redlich-Kwong (RK) and Redlich-Kwong-Soave (RKS)
equations
Like Peng-Robinson, the Redlich-Kwong and Redlich-Kwong-Soave
equationand its variants are examples of simple cubic equations of state.
Advanced Equation of state options

The advanced implementation of both the Peng-Robinson and the Redlich-
Kwong-Soave equations of state (PRA and RKSA models) contain additional
non-standard features. These include the ability to match stored values for the
liquid density and the saturated vapour pressure and a choice of mixing rule.
The Peneloux density correction

This correlation is used to match the density calculated from the equation of state
to that stored in the chosen physical property data system. For light gases, the
density is matched at a reduced temperature of 0.7 and the volume correction is
assumed constant. For liquid components the volume shift is treated as a linear
function of temperature; the density is matched at 290.7K and 315.7K so as to
reproduce the density and thermal expansivity of liquids over a range of
temperatures centred on ambient.
Fitting the vapour pressure curve

For each component the constants are fitted by linear regression to the vapour
pressure over a range of reduced temperatures corresponding to the stored data.
Fewer than 5 coefficients will be fitted if there is insufficient data or if the
extrapolation to low temperatures is unrealistic. If the vapour pressure is
undefined, the correlation reverts to the standard equation for that component.
Mixing Rules
For highly non-ideal systems it is often useful to be able to use a Gibbs energy
excess model(e.g. UNIQUAC or NRTL) as part of the mixing rule for the
equation of state. The possibilities are outlined in the separate "Models and
Physical Properties Guide".
When to use cubic equations of state

The simple cubic equations of state, PR and RKS, are widely used in engineering
calculations. They require limited pure component data and are robust and
efficient. Both PR and RKS are used in gas-processing, refinery and
petrochemical applications. They will usually give broadly similar results,
although if one model has been fitted to experimental data and there are no
interaction parameters for the other then the optimised model is always
preferable. There is some evidence that RKS gives better fugacities and PR
better volumes (densities) but both can be improved if the Peneloux correction is
used.
For most applications we would recommend the use of the RKSA (or PRA)
model sets which use the Peneloux correction, fit a to the vapour pressure and
use the Van der Waals 1-fluid mixing rules.
RKSA with the Infochem mixing rules is used as part of the hydrate model and
provides extra flexibility to represent the highly non-ideal polar systems. It does,
however, require suitable BIPs for such systems.
The API variant of RKS is applicable to petroleum systems and mixtures
containing hydrogen, while RK may be used instead of ideal gas model for the

vapour phase of systems where the liquid phase is being modelled with an
activity coefficient model.
Cubic plus association (CPA) model

The CPA model consists of the Redlich-Kwong-Soave equation plus an
additional term based on Wertheims theory that represents the effect of
chemical association.
The CPA model also uses the Peneloux density correction to match the liquid
density calculated from the equation of state to that stored in the chosen physical
property data system at a reduced temperature of 0.7 or at 298.15K, whichever
temperature is the lower.
When to use CPA.

The CPA model may be used for hydrate calculations with methanol, MEG and
salt inhibition as these are the only cases for which parameters are currently
provided. This will be extended in future versions
PC-SAFT equation of state..

The PC-SAFT equation is a development of the SAFT model that has been
shown to give good results for a wide range of polar and non-polar substances
including polymers. Polymers is one of the most important areas of application
of PC-SAFT. The model appears to be one of the most accurate and realistic
equations of state currently available for modelling polymer systems.
PC-SAFT stands for the Perturbed Chain Statistical Associating Fluid Theory
and it incorporates current ideas of how to model accurately the detailed
thermodynamics of fluids within the framework an equation of state. The
mathematical structure is very complex and cannot be conveniently described in
a manual. However, references where this information may be found are given
on out "Models and Physical Properties Guide".
The Multiflash version includes an implementation of the association term of
PC-SAFT which follows the same general structure as the association term in the
CPA model.
Polymers are not well defined chemical compounds but rather a distribution of
chain molecules of varying molecular weight. In Multiflash, polymers must be
represented by one or more pseudocomponents which must be set up as user-
defined components.
Using PC-SAFT, every pseudocomponent for a given polymer must be assigned
the same values of the pure-compound parameters SAFTSIGMA (in metres, not
ngstrom units) and SAFTEK. In addition, the SAFTM parameter must be
specified. This is normally quoted as a ratio to the molecular weight, so it has to
be calculated for each polymer pseudocomponent knowing the molecular weight.
For polystyrene, for example, Gross and Sadowski give the ratio as 0.019, so for
a polystyrene pseudocomponent of molecular weight 100000, the SAFTM
parameter should be set to 1000000.019=1900, etc.
Values of PC-SAFT parameters for polymers can be found in Modeling Polymer
Systems Using the Perturbed-Chain Statistical Associating Fluid Theory
Equation of State by Gross and Sadowski in Industrial and Engineering
Chemistry Research, 41, 1084, (2002) and in Modeling of polymer phase
equilibria using Perturbed-Chain SAFT by Tumakaka, Gross and Sadowski in
Fluid Phase Equilibria, 194-197, 541, (2002).
Multiflash also has a version of PC-SAFT with simplified mixing rules as
proposed by researchers at the Danish Technical University. The same pure
component parameters can be used for this model variant but the model
interaction parameters will be different.

PSRK equation of state
This model consists of the RKSA equation of state with vapour pressure fitting,
the Peneloux volume correction and the PSRK type mixing rules. The excess
Gibbs energy is provided by the PSRK variant of the Unifac method. This is the
same as the normal VLE Unifac model except that the group table has been
extended to include a large number of common light gases.
When to use PSRK

The PSRK model is an extension of the Unifac method. It is intended to predict
the phase behaviour of a wide range of polar mixtures using the solution of
groups concept as embodied in Unifac. The main benefit of PSRK is that it is
able to handle mixtures containing gases much better than Unifac and unlike a
normal equation of state it can handle polar liquids. This is because (a) it uses an
equation of state with an excess Gibbs energy mixing rules thereby avoiding
problems of how to handle supercritical components in an activity coefficient
equation; (b) the Unifac group parameter table has been extended in PSRK to
include 32 common light gases.
LCVM equation of state

This model consists of the PRA equation of state with vapour pressure fitting,
the Peneloux volume correction and the LCVM type mixing rules. The excess
Gibbs energy is provided by the LCVM variant of the Unifac method. This is the
same as the normal VLE Unifac model except that the group table has been
extended to include a number of common light gases found in petroleum fluids.
When to use LCVM

The LCVM model is an extension of the Unifac method. It is intended to predict
the phase behaviour of petroleum fluids mixed with polar compounds using the
solution of groups concept as embodied in Unifac. The main benefit of LCVM is
that it is better able to handle asymmetric mixtures. This is because it uses an
equation of state with an excess Gibbs energy mixing rule that was specifically
designed to work with Unifac for mixtures of light gases and heavy
hydrocarbons.
Lee-Kesler-Plcker (LKP) equation of state

The LKP method is a 3 parameter corresponding states method based on
interpolating the reduced properties of a mixture between those of two reference
substances
When to use LKP

The method predicts fugacity coefficients, thermal properties and volumetric
properties of a mixture. However, it is rather slow and complex compared to the
cubic equations of state and is not recommended for phase equilibrium
calculations, although it can yield accurate predictions for density and enthalpy.
It would normally be applied to non-polar or mildly polar mixtures such as
hydrocarbons and light gases.
Benedict-Webb-Rubin-Starling (BWRS) equation of state

The BWRS equation method is an 11 parameter non-cubic equation of state. For
methane, ethane, ethylene, propane, propylene, isobutane, n-butane, isopentane,
n-pentane, hexane, heptane, octane, carbon dioxide, hydrogen sulphide and
carbon dioxide, the pure component parameters are set to values recommended
by Starling in his book Fluid Thermodynamic Properties for Light Petroleum

Systems, Gulf Publishing Co., Houston, 1973. For other substances the pure
component parameters are estimated using correlations developed by Starling
and Han which are given in the same book.
When to use the BWRS equation

The BWRS equation gives much more accurate volumetric and thermal property
predictions for light gases and hydrocarbons. Given suitable interaction
parameters it should give reasonable vapour-liquid phase equilibrium predictions
but owing to its complexity, it requires more computing time than the cubic
equations of state.
Multi-reference fluid corresponding states (CSM) model

The CSM model is based on a collection of very accurate equations of state for a
number of reference fluids. It will provide accurate values of properties for any
of the reference fluids (see below for a list) and it uses a 1-fluid corresponding
states approach to estimate mixture properties. It is formulated so that mixture
properties will reduce to the (accurate) pure component values as the mixture
composition approaches each of the pure component limits.
Reference fluids
The current model implementation includes reference equations of state for the
following substances: argon, iso-butane, n-butane, CO, CO2 , ethane, ethylene,
fluorine, H2S, hydrogen, methane, nitrogen, octane, oxygen, n-pentane, propane,
water (IAPSW 95), xenon, helium, hexane, heptane, octane, ammonia, neon,
propylene, R123, R152a, R124, R125, R134a, R22, R32, R11, R113, R114,
R115, R116, R12, R13, R14, R23, and RC318. Hydrocarbons between pentane
and octane are modelled as combinations of these substances. The equations of
state are taken from various sources and do not all have the same quality or
range of applicability.
Applicability.
The model is very accurate for pure substances that are included in the above list
of reference substances. It is also applicable to near-ideal mixtures such as air
but for the best results it is necessary to fit values of the binary interaction
parameters to match experimental data. The model should not be used for non-
ideal mixtures such as water + CO2 etc.
Activity coefficient methods

In an ideal liquid solution the liquid fugacity of each component in the mixture is
directly proportional to the mole fraction of the component
f i l = xi f i *,l
The ideal solution assumes that all molecules in the liquid solution are identical
in size and are randomly distributed. This assumption is valid for mixtures made
up of molecules of similar size and type, but for mixtures of unlike molecules
you must expect varying degrees of non-ideality. The activity coefficient, i ,
represents the deviation of the mixture from ideality, as defined by the ideal
solution.

Activity coefficient equations in Multiflash
A number of activity coefficient equations are available in Multiflash. Details of
each model may be found in the separate "Models and Physical Properties
Guide".
Ideal solution model

The ideal solution model may be used when the mixture is ideal, i.e. when there
are no mixing effects. It can also be used for single components to calculate
some pure component properties from the physical property databank.
Wilson E equation
This model may be used for vapour-liquid equilibrium calculations but it is not
capable of predicting liquid-liquid immiscibility. Binary interaction parameters
are provided in our INFOBIPS bank for some component pairs. If no BIPs are
included for your particular mixture then to obtain accurate predictions you must
supply binary interaction parameters values in the correct units, which are Jmol-
1
.
Wilson A equation,
This model, which is a simplified form of the Wilson E model, may be used for
vapour-liquid equilibrium calculations but it is not capable of predicting liquid-
liquid immiscibility. To obtain accurate predictions you must supply binary
interaction parameters (BIP) values, which are dimensionless.
NRTL equation
The NRTL model may be used for vapour-liquid, liquid-liquid and vapour-
liquid-liquid calculations (the VLE option should be used for VLLE). Again if
BIP values are not provided in the BIP databank, INFOBIPS, they must be
supplied for accurate predictions. In cases where the user does not specify any
value for the third adjustable parameter, ij , it is automatically set to 0.3 if the
VLE version of NRTL is specified or to 0.2 if the LLE version is specified.
Note that ij = ji so only ij need be supplied.
UNIQUAC equation
The UNIQUAC model may be used for vapour-liquid, liquid-liquid and vapour-
liquid-liquid calculations. There are UNIQUAC VLE and LLE variants as for
the NRTL equation. Again BIP values must be supplied for accurate predictions
if they are not included in INFOBIPS. For VLLE the variant chosen should be
guided by the BIPs available.
Regular Solution theory

Regular solution theory can be used for vapour-liquid calculations for mixtures
of non-polar or slightly polar components. The theory is applicable to systems
which exhibit negligible entropies and volumes of mixing. However, it has been
largely superseded by equations of state.
Flory-Huggins
The Multiflash implementation of Flory-Huggins theory includes a regular
solution correction term. The Multiflash expression reduces to the standard
Flory-Huggins theory if all interactions parameters are set to unity. However, to
obtain reasonable results it is usually necessary to adjust the values of the
interaction parameters to fit the data.

Flory-Huggins theory is able to describe systems which include some long chain
molecules. It has consequently applied to model polymer systems but it has been
largely superseded by other models such as PC-SAFT
UNIFAC method
The UNIFAC method is similar to UNIQUAC but the interaction parameters are
predicted based on the molecular group structure of the components in the
mixture. The is completely predictive and does not require the user to supply
BIPs.
Dortmund Modified UNIFAC method

For Dortmund modified UNIFAC, the two binary parameters between
components and are treated as quadratic functions of temperature.
Dortmund modified UNIFAC is better able to represent the simultaneous
vapour-liquid equilibria, liquid-liquid equilibria and excess enthalpies of polar
mixtures than the original UNIFAC method. Like original UNIFAC, however, it
does not allow for the presence of light gases in the mixture.
Gas phase models for activity coefficient

methods
The normal choices for the gas phase model would be the perfect gas equation,
the RK equation of state or a virial equation of state. They are described in
detail in the separate "Models and Physical Properties Guide".
A second virial coefficient model such as Hayden and O'Connell (HOC) can
account for gas phase non-idealities up to pressures of about 5 to 10 bar. The
implementation of the HOC model in Multiflash allows the vapour phase
association of substances such as acetic acid to be represented.
When to use activity coefficient models

Activity coefficient models are usually used to modelany combination of polar
and non-polar compounds including those exhibiting very strong non-ideality. If
the gas phase model is ideal then pressures should be limited to 3-5 bar. If
Redlich-Kwong or another equation of state is used to model the gas phase then
the pressure limit is higher, of the order of 10-20 bar. However, the mixture
should be subcritical. If the mixture contains some components which are above
their critical point, such as dissolved gases, then you should be aware that the
properties of components, e.g. vapour pressure, will be extrapolated.
NRTL, UNIQUAC and UNIFAC may be used to model VLE, LLE and VLLE
but both Wilson models are limited to VLE only.
To obtain accurate predictions from any of the activity coefficient models,
except UNIFAC, it is necessary to use interaction parameters. If these are not
available in INFOBIPS for your system the you need to supply interaction
parameters for the missing values which match the model specification given
above and which are in the correct units. Multiflash uses standard SI units, Jmol-
1
, for BIPs, except for Wilson A where the BIPs are dimensionless.
Models for solid phases

Multiflash may also be used to calculate the phase equilibrium of systems
containing solid phases, either mixed or pure. These may occur either when a
normal fluid freezes or may be a particular type of solid phase such as a hydrate.

Solid freeze-out model
This model is used to calculate the thermodynamic properties of pure solid
phases formed by freezing one or more of the components in the fluid mixture.
It may be applied to any component where this may be a consideration.
Solid freeze-out can be used to model the solidification of compounds such as
water, carbon dioxide or methane, for example in natural gases. It can also be
used to model eutectics.
Modelling hydrate formation and inhibition

Natural gas hydrates are solid ice-like compounds of water and the light
components of natural gas. They form at temperatures above the ice point and
are therefore a serious concern in oil and gas processing operations. The phase
behaviour of systems involving hydrates can be very complex because up to
seven phases must normally be considered. The behaviour is particularly com
plex if there is significant mutual solubility between phases, e.g. when inhibitors
or CO2 are present. Multiflash offers a powerful set of thermody namic models
and calculation techniques for modelling gas hydrates.
Hydrate model
The original Infochem model uses a modification of the RKS equation of state
for the fluid phases plus the van der Waals and Platteeuw model for the hydrate
phases. An alternative model uses the CPA model for the fluid phases. The
hydrate models have also been extended to include hydrate structure H in
addition to structures I and II. The model can explicitly represent all the effects
of the presence of inhibitors, although parameters for the CPA model are only
provided for methanol, MEG and salt. CPA parameters for additional
thermodynamic inhibitors will be added in future versions.
The main features of the models are:
Our description of hydrate phase behaviour uses a
thermodynamically consistent set of models for all phases present
including hydrate structures I, II and H, ice, water, liquid and gas.
The vapour pressures of pure water and sublimation pressures of
ice are very accurately reproduced.
The following natural gas hydrate formers are included: methane,
ethane, propane, isobutane, butane, nitrogen, CO2 and H2S.
Other hydrate formers that are not usually present in natural gas but
which form structure I or II are also included. These compounds
are: SF6 , ethylene, propylene, cyclopropane, oxygen, argon,
krypton and xenon.
Parameters are provided for the following compounds that form
hydrate structure II in the presence of small help-gases such as
methane or nitrogen: cyclopentane, benzene and neopentane. These
compounds and the structure H formers listed below may be
present in condensate and oil systems.
Structure H hydrates form in the presence of small help-gases
such as methane or nitrogen but the formation temperatures are
significantly higher (about 10 K) than pure methane or nitrogen
hydrate. In practice it seems that structure II hydrates form before
structure H but if there is enough water structure H may be formed
too. The structure H model includes parameters for:
isopentane

neohexane
2,3-dimethylbutane
2,2,3-trimethylbutane
2,2-dimethylpentane
3,3-dimethylpentane
methylcyclopentane
methylcyclohexane
cis-1,2-dimethylcyclohexane
2,3-dimethyl-1-butene
3,3-dimethyl-1-butene
cycloheptene
cis-cyclooctene
adamantane
ethylcyclopentane
1,1-dimethylcyclohexane
ethylcyclohexane
cyclohexane
cycloheptane
cyclooctane
The thermal properties (enthalpies and entropies) of the hydrates
and ice are included permitting isenthalpic and isentropic flashes
involving these phases.
Calculations can be made for any possible combination of phases
including cases without free water. No modification of the phase
models is required to do this.
The properties of the hydrates have been fixed by investigating
data for natural gas components in both simple and mixed hydrates
to obtain reli able predictions of structure I, structure II and
structure H hydrates.
The properties of the empty hydrate lattices have been investigated
and the most reliable values have been adopted.
Proper allowance has been made for the solubilities of the gases in
water so that the model parameters are not distorted by this effect.
This is particularly important for carbon dioxide and hydrogen
sulphide which are relatively soluble in water.
Correct thermodynamic calculations of the most stable hydrate
structure have been made.
The model is used to calculate the hydrate equilibrium formation temperature at
a given pressure or pressure at a given temperature where the first very small
quantity of hydrate appears after a sufficiently long time. This point corresponds
to the thermodynamic formation point, also known as the hydrate dissociation
point. Before the thermodynamic formation point is reached hydrate cannot
form - this point is also called the stability limit. Beyond the stability limit
hydrate can form but may not do so for a long time.
The model has been tested on a wide selection of open literature and proprietary
experimental data. In most cases the hydrate dissociation temperature is
predicted to within 1K.
Hydrates in water sub-saturated systems

Hydrates can form even in systems where there is no free water present. Our
hydrate model, with both RKSAINFO and CPA used to model the fluid phase, is
capable of modelling this, although the data available for validating the results
are very limited. What we have noticed is that for systems with very little water
and at high pressures the predicted hydrate dissociation temperatures using

RKSAINFO and CPA tend to diverge with increasing pressure, with CPA
predicting lower hydrate dissociation temperatures than RKSAINFO. There are
no data presently available to confirm which is correct. If this causes any
difficulty it is possible to reproduce the CPA predictions with RKSAINFO by
using parameters which reduce the Infochem mixing rule to van der Waals.
These parameters, for methane, ethane and propane with water, are stored in the
file vdwbip.mfc. They can be used to overwrite the existing BIPs for these
binaries by loading this file after you have defined the hydrate model based on
RKSAINFO as the fluid model.
When compared to the available data all three possible variants (CPA,
RKSAINFO with standard and vdw BIP) give hydrate dissociation results within
experimental error.
Nucleation model
The nucleation model was developed in collaboration with BP as part of the
EUCHARIS joint venture. This model is an extension of the existing
thermodynamic model for hydrates described above. In order to extend the
nucleation model into the Multiflash program, the following enhancements to the
nucleation model were made:
The model was extended to cover the homogeneous nucleation of
ice and fitted to available ice nucleation data.
The model was generalised to cover in principle nucleation from
any liquid or gas phase.
A correction for heterogeneous nucleation was included that was
matched to available hydrate nucleation data.
An improved expression was adopted for fluid diffusion rates.
More robust numerical methods were introduced into the program.
The nucleation model provides an estimate of the temperature or pressure at
which hydrates can be realistically expected to form. The model is based on the
statistical theory of nucleation in multicomponent systems. Although there are
limitations and approximations involved in this approach it has the major benefit
that a practical nucleation model can be incorporated within the framework of a
traditional thermodynamic hydrate modelling package.
Many of the comparisons of model predictions with experimental data have been
made. In general measurements of hydrate nucleation result in an experimental
error of 2C and predictions are usually within this error band.
With the existing Infochem hydrate model and the nucleation model, the hydrate
formation and dissociation boundaries can be predicted between which is the
hydrate formation risk area.
Inhibitor modelling
Thermodynamic hydrate inhibitors decrease the temperature or increase the
pressure at which hydrates will form from a given gas mixture. The original
Infochem hydrate model includes parameters for the commonly used inhibitors:
methanol, salts, and the glycols MEG, DEG and TEG and for the less well-tested
inhibitors ethanol, iso-propanol, propylene glycol and glycerol. A new mixing
rule was developed for the SRK equation of state to model the effects of the
inhibitors on the fluid phases.
The hydrate model using CPA to model the fluid phases is limited in the current
version of Multiflash to hydrate calculations with pure water or with methanol,
MEG and salt. Additional parameters to extend the CPA model to cover the full
range of thermodynamic inhibitors listed above will be included in future
versions.

The treatment of hydrate inhibition has the following features:
The model can explicitly represent all the effects of inhibitors
including the depression of the hydrate formation temperature, the
depression of the freezing point of water, the reduction in the
vapour pressure of water (i.e. the dehydrating effect) and the
partitioning of water and inhibitor between the oil, gas and aqueous
phases.
The model has been developed using all available data for mixtures
of water with methanol, MEG, DEG and TEG. This involves
representing simultane ously hydrate dissociation temperatures,
depression of freezing point data and vapour-liquid equilibrium
data.
Two salt inhibition models are available. The older model is based
on a salt component. The new model is a (restricted) electrolyte
model. A salinity calculator tool is provided ( see Salt calculator
on page 81 ) which allows the salt composition to be entered in a
variety of units and calculates the equivalent amount of sodium
chloride in the mixture. The equivalent composition is based on the
freezing point depression and hydrate inhibition effect of the salts.
The solubilities of hydrocarbons and light gases in water/inhibitor
mixtures have also been represented.
The original binary interaction parameters for the RKSA fluid model stored for
alkanes with MEG correctly reproduce all the reported data for alkane solubility
in MEG, for MEG solubility in heptane and the inhibition effect of MEG on
hydrate dissociation temperatures. However, the measured data for MEG
solubility in alkanes is limited to a single data set for the solubility of MEG in
heptane. For mixtures containing hydrocarbons greater than C7 the parameters
in versions prior to 2.9 predicted an increasing MEG solubility with increasing
carbon number. This may have led to over prediction of the amount of MEG
required to inhibit hydrates for heavy crude oils.
Later versions of Multiflash include new parameters for alkanes with MEG
which stabilise the solubility of MEG in higher alkanes and correctly reproduce
the MEG inhibition effect on hydrates. However, they fail to predict the correct
solubility of alkanes in MEG. The new parameters were included in the BIP
databank, oilandgas4, which is still the current version.. If, for any reason, you
wish to use the original parameters you can still retrieve these from the BIP
databank, oilandgas3. For information on how to do this see Supplementing or
overwriting BIPs on page 56.
Salinity Model
Both salinity models operate at present on a sodium chloride equivalent basis.
The salt component model represents the effect of sodium chloride in aqueous
solution by a special equation of state component called salt component or
saltcomp. This model is designed to operate with the Advanced RKS equation
although it is also usable with the Advanced PR equation. The salt component
model cannot be used with the CPA model or any other equation of state.
The new electrolyte model is designed to be added on to any equation of state.
The models selection form allows it to be selected for use with the Advanced
RKS equation and the CPA model. It represents sodium chloride as a equimolar
combination of sodium and chloride ions. Future versions of Multiflash will
extend this to other ions.

Modelling wax deposition
Waxes are complex mixtures of solid hydrocarbons that freeze out of crude oils
if the temperature is low enough. Under conditions of interest to the oil industry,
waxes consist mainly of normal paraffins. Waxes are thought to consist of many
crystals each of which is a solid solution of n-paraffins of a fairly narrow range
in molecular weight.
Multiflash contains two wax models, the Coutinho model and the multisolid
model. The features of the Coutinho model are:
The Coutinho model represents wax as a solid solution. There are two
versions of the model, the Wilson and Uniquac variants. The version
normally selected in Multiflash is the Wilson model which approximates
the wax as a single solid solution. This approach is relatively simple to
apply and gives a good representation of the data, so it is recommended
for general engineering use. The more complex Uniquac variant models
the tendency of waxes to split into several separate solid solution phases.
The Uniquac variant can be activated by configuration files that can be
supplied by Infochem for users who wish to simulate the detailed physical
chemistry of wax precipitation.
The model gives good predictions of waxing behaviour, both wax
appearance temperature and the amount of wax precipitated at different
temperatures. The method is applicable to both live and dead oils.
The model requires that the normal paraffins are explicitly present in the
fluid model, as these are the wax forming components. The user must
therefore use the new characterisation method either to enter the
measured n-paraffin concentrations or else to estimate the n-paraffin
distribution. The composition of the wax phase is determined by the
known thermal properties (normal melting point, enthalpy of fusion, etc.)
of the n-paraffins combined with their solution behaviour in both oil and
wax phases.
In principle the wax model can be used in conjunction with any
conventional cubic equations of state. The default options in the
Multiflash implementation is RKSA.
The multisolid wax model is still available as an alternative option. The features
of this model are:
It approximates waxing behaviour by representing the wax as a mixture of
separate phases, each one of which corresponds to a pure pseudocomponent from
the equation of state model. The composition of the wax phase is determined by
the assumed thermodynamic properties (normal melting point, enthalpy of
fusion, etc.) for the petroleum fractions heavier than C6 but which are not
asphaltenes and resins.
The multisolid wax model should be used in conjunction with conventional
cubic equations of state. The default option from the usual model set selection is
RKSA but the multisolid model with PRA may be accessed from the waxpra.mfc
file.
The original Infochem oil characterisation method should be used in conjunction
with the multisolid wax model, as the model was set up to be compatible with
this method. We recommend that the oil should be represented by 15
pseudocomponents and the RKSA model should be selected.
Modelling asphaltene flocculation

Asphaltenes are polar compounds which are stabilised in crude oil by the
presence of resins. If the oil is diluted by light hydrocarbons, the concen tration
of resins goes down and a point may be reached where the asphaltene is no
longer stabilised and it flocculates to form a solid deposit. Because the

stabilising action of the resins works through the mechanism of polar
interactions, their effect becomes weaker as the tem perature rises, i.e.
flocculation may occur as the temperature increases. However, as the
temperature increases further the asphaltene becomes more soluble in the oil.
Thus, depending on the temperature and the com position of the oil, it is possible
to find cases where flocculation both increases and decreases with increasing
temperature.
The asphaltene model is based on the RKSA cubic equation of state with addi
tional terms to describe the association of asphaltene molecules and their
solvation by resin molecules. The interactions between asphaltenes and
asphaltenes-resins are characterised by two temperature-dependent association
constants: K AA and K AR . The remaining components are de scribed by the van
der Waals 1-fluid mixing rule with the usual binary in teraction parameters k ij
so the asphaltene model is completely compatible with existing engineering
approaches that are adequate for describing vapour-liquid equilibria. The model
is a computationally-efficient way of in corporating complex chemical effects
into a cubic equa tion of state.
Other thermodynamic models

Multiflash also incorporates a corresponding states method for estimating the
density of liquid mixtures, the COSTALD model.
The COSTALD method can provide very accurate volumes for pure substances
and simple mixtures, such as LNG. It is valid for liquids on the saturation line
and compressed liquids up to a reduced temperature of 0.9. It is not necessarily
accurate for heavy hydrocarbon mixtures with dissolved gases.
Transport property models

For each of the transport properties, viscosity, thermal conductivity and surface
tension, Multiflash offers two approaches to obtaining values for mixtures. One
route is to calculate the property for a mixture by combining the property values
for the pure components of which it is composed; the mixing rule approach. The
other is to use a predictive method suitable for the property in question.
Viscosity
Pedersen Model
This is a predictive corresponding states model originally developed for oil and
gas systems. It is based on accurate correlations for the viscosity and density of
the reference substance which is methane. The model is applicable to both gas
and liquid phases. The Infochem implementation of the Pedersen model includes
modifications to ensure that the viscosity of liquid water, methanol, ethanol,
MEG, DEG and TEG and aqueous solutions of these components or salt are
predicted reasonably well. We would recommend this method for oil and gas
applications. It is the default viscosity model for use with equations of state.
Reference: Pedersen, Fredenslund and Thomassen, Properties of Oils and
Natural Gases, Gulf Publishing Co., (1989).
Twu Model
This is a predictive modelsuitable for oils. It is based on a correlation of the API
nomograph for kinematic viscosity plus a mixing rule for blending oils. It is only
applicable to liquids.

Reference: Twu, Generalised method for predicting viscosities of petroleum
fractions, AIChE Journal, 32, 2091, (1986).
Lohrenz-Bray-Clark method
This modelis a predictive model which relates gas and liquid densities to a fourth
degree polynomial in reduced density.
In Multiflash the fluid densities are derived from any chosen equation of state,
rather than the correlations proposed by Lohrentz et al. This has the advantage
that there is no discontinuity in the dense phase region when moving between
liquid-like and gas-like regions.
Multiflash also allows two variants of the LBC model. The first uses the original
LBC method to estimate the critical volume of petroleum fractions and takes the
critical volume of other components from the chosen data source. The second
variant fits the critical volume of each component to reproduce the liquid
viscosity at the boiling point.
The method is mainly applicable to the types of components found in oil and gas
processing but we would recommend that the Pedersen method is normally used
in these cases.
Liquid viscosity mixing rule

This method obtains the liquid mixture viscosity by applying a simple mixing
rule to the pure component saturated liquid viscosities generated from a
databank. Each component in the mixture must have a liquid viscosity
correlation stored in the databank.
Vapour viscosity mixing rule

The viscosity of a gas mixture at low density is calculated from the databank
correlations for the zero pressure gas viscosities of the pure components. Each
component in the mixture must have a vapour viscosity correlation stored in the
databank.
Thermal conductivity
Chung-Lee-Starling thermal conductivity method

This is a predictive method for both gas and liquid mixture thermal
conductivities. It requires the critical properties, Tci , Vci and ci for non-polar
components. For polar and associating fluids the dipole moment and an
association parameter are also required. Association parameters for water, acetic
acid and the lower alcohols are provided. The fluid density is required as part of
the calculation and this quantity may be obtained from any of the
thermodynamic models in Multiflash. This method can be used for oil and gas
processing and also for polar mixtures.
Liquid thermal conductivity mixing rule

This method obtains the liquid mixture thermal conductivity by applying a
simple mixing rule to the pure component saturated liquid thermal conductivities
generated from a databank. Each component in the mixture must have a liquid
thermal conductivity correlation stored in the databank.

Vapour thermal conductivity mixing rule
The thermal conductivity of a gas mixture at low density is calculated from the
correlations for zero density gas thermal conductivity of the pure components at
the same temperature.
Surface Tension
Macleod-Sugden method
This method predicts the surface tension of a liquid mixture based on the pure
component parachors stored in a databank. It is mainly applicable to the types of
component found in oil and gas processing.
Reference: Pedersen, Fredenslund and Thomassen, Properties of Oils and
Natural Gases, Gulf Publishing Co., (1989).
Surface tension mixing rule

The surface tension for a liquid mixture may be calculated from the correlations
for the surface tension of the pure saturated liquids at the same temperature and
pressure using a power law model.
Diffusion coefficient
Fuller method
The Fuller method calculates gas diffusion coefficients. It is an empirical
modification of Chapman-Enskog theory.
Hayduk-Minhas method
The Hayduk-Minhas method calculates liquid diffusion coefficients. It consists
of a number of empirical correlations for different classes of mixture.
How to specify models in Multiflash

There are three ways by which models can be specified in Multiflash. The
model can be defined as part of a complete problem setup file, extension .mfl.
Loading a complete problem setup file was described earlier as part of the
simple tutorial, Loading a problem setup file on page 21. The model can also
be easily specified through the menu options (as a model set or freeze-out
components to model pure solid phases such as ice) or by loading a model
configuration file, extension .mfc, which defines the model only, not the
complete problem.
How to load a model

Loading the model definition is usually the first step in setting up a problem.
The model may be specified from the menu or by loading a model configuration
file or it may be included in the problem setup file.
Defining the model from the menu

To define the model from the menu bar first
Select Select, then

Select Model set and click on it. If this is the fist time it has been called in any
Multiflash run the Select Model Set dialog box will appear with its default
option set to Equations of State. The dialog box includes a list of the
thermodynamic models, a list of possible phase descriptors, a choice of model
sets for the transport properties and the ability to include difusivity calculations.
Models for other options, such as

Activity Models
Hydrates
Waxes
Asphaltenes
Combined solids
may by defined by clicking on the appropriate tab when similar dialog boxes
will be activated.
The Select Model Set will reflect, as far as possible, the model setting in the
problem file loaded.
The default for a model, other than the activity models, is to include four phase
descriptors, gas, liquid1, liquid2 and water and use the Pedersen. CLS and
Macleod-Sugden set of transport property models. You may select any of the
other sets of transport models if you wish, or None if you dont wish to calculate
any transport properties. You may limit the number of phases to be considered.
For example, you may know that your problem has only a gas and one possible
liquid phase. In this case defining only gas and liquid1 may speed up calculation
.
Once you are satisfied with your model selection click the Define Model button.
The model should load immediately and you will see a message to confirm this,
for example:

The message that the model has been successfully loaded will also be displayed
in the results window and sent to the log file. Click OK to go back to the model
definition dialog box, and then click Close to return to the main Multiflash
window.
To redefine models, repeat the steps as described above. The previous model set
will be overwritten automatically.
Each model set contains a complete definition of the thermodynamic and
transport property models and a list of phases, including key components for that
phase.
Defining the model from a model configuration file

If you prefer you can load a model definition from a model configuration file,
extension .mfc. Model configuration files are supplied for all the model options
available in Multiflash. Each one contains exactly the same information as the
model set, with the addition that the pure component data source is preset to be
INFODATA. Like all Multiflash input files the model configuration file may
also include comments.
The content of the .mfc file is displayed in the results window. If the model is
not loaded successfully for any reason a message box appears and detailed error
messages are displayed in the results window.
What the model definition means

It is not necessary to understand the Multiflash model definition to carry out
useful calculations. The explanation in this section is provided so that you can
refer to the details when you need to. For example you may wish to change the
key component for a phase.
In the example below the model is Peng-Robinson. The definition of a model
configuration file will appear in the results window and includes:
The source of pure component data, binary interaction parameters and petroleum
fraction correlations
Puredata infodata;
bipdata infobips oilandgas;
chardata infochar tbsoereide;
A command to remove all previously loaded models and binary interaction

parameters:
remove models; remove bipsets;
A command to allow for the possibility of user supplied BIPs which are
identified by the name PRBIP
bipset PRBIP 1 constant;
The definition of the thermodynamic model; consists of the command model
followed by a model name, MPR, and a keyword to identify the model, PR and
finally the name for a user supplied BIP set, PRBIP.
model MPR PR PRBIP;
The definition of the default models used for the transport properties:
model MPDVISC pdvisc lfit;
model MCLSMPR cls MPR; model MMCSMPR mcs MPR;
A phase descriptor giving an identifier and a phase type for each possible phase
which may be considered in the calculation:

remove pd;
pd Gas gas MPR * * MPDVISC MCLSMPR;
pd Liquid1 liquid MPR * * MPDVISC MCLSMPR MMCSMPR;
pd Liquid2 liquid MPR * * MPDVISC MCLSMPR MMCSMPR;
pd Water liquid MPR * * MPDVISC MCLSMPR MMCSMPR;
and finally, specification of a key component for each liquid phase so that it can
be identified when multiple liquid phases are found.
key Water 007732-18-5;
key Liquid1 not 007732-18-5;
key Liquid2 not 007732-18-5;
The CAS number is that for water. This format is general and unambiguous and
allows, for instance, for cases where the user has chosen the alternative H2O for
water. However, Multiflash will still recognise the original format of
Key Water water;
With the model successfully loaded you can continue to specify other aspects of
the problem such as the components and conditions.
For more information on commands see the Appendix to the printed User Guide.
How to change a model

You may wish to compare the predictions from one model with those from
another. This is easily achieved. Each model set or model configuration file
contains the commands to remove all currently defined models, phase
descriptors and BIPs. For example, all you need to do to change from using
Peng-Robinson to RKS is to
Click on RKS in the Select Models dialogue box or
Load the RKS.mfc file.
Either of these actions will remove the previous model definition and load a new
one and you are ready to repeat your earlier calculation with a new model or
define a new problem.
Similarly you may change the default method for calculating the transport
properties.
Loading hydrate models

If you define hydrate models using model configuration files such as
hydrate.mfc and hydrateh.mfc, a complete set of models and phases descriptors
will be specified. However, specifying hydrate models through the Select Model
Set option allows selection of the different forms of hydrate individually.
To define a hydrate model first
Select Select/Model Set from menu bar.
Select Hydrates tab to activate the Hydrates dialog box.

The user can define the fluid phase model to be used. The RKSA(Infochem)
fluid phase model has parameters defined for several inhibitors, including salt
calculated using the original Salt Model, see Modelling hydrate formation and
inhibition on page 37. The CPA-Infochem fluid phase model was introduced to
improve predictions of inhibitor partitioning, with parameters provided for
methanol and MEG. Two Salt models have been implmented. The latest Salt
Model , based on an electrolyte approach can be used with either
RKSA(Infochem) or CPA as the fluid phase model and is accessed by selecting
the + Electrolyte options. Both Salt Models are described in Modelling
hydrate formation and inhibition on page 55.
The default settting is to include models for both Hydrate 1 and Hydrate 2. In the
majority of cases for natural gases, condensates or oils Hydrate 2 is the most
stable hydrate form. However, there are some fluids, with certain compositions
such as those containing high proportions of methane or H2S, where the most
stable hydrate structure can change from Hydrate 2 at low pressures to Hydrate 1
at high pressures. If you also want to consider Hydrate H being formed you
select this as an additional option.
Calculation of the hydrate dissociation temperature and pressure will be quicker
if you exclude the hydrate nucleation option. However, If you also want to
include the nucleation model select Phase Nucleation from the list of phase
descriptors.
As before Click the Define Model button and a message saying the model has
been successfully defined will appear. Click OK for the model and phases
specification to be reflected in the main window.
Click the Close button to get back to the main screen. You can check which
models are defined at any stage by using the Tools/Show/Models menu option.
The models currently available will be listed in the results window.
The Freeze-out model

The freeze-out model can be applied to any component. To apply the model to a
component in a stream you need to define the component using the
Select/Freeze-out component option. To do this
Click on Freeze-out components from the Select menu
This will produce a window displaying the components in the stream, e.g.

Checking the adjacent box allows you to add or remove the freeze-out model for
any number of components within the overall limit on the total number of
phases, which is nine.
The command will be reflected in the main window and show the name allocated
to the solid phase. By default this sill be solid plus the compound name except
in the case of water where it will be ice, e.g.
Freeze-out Model
pd "SOLIDDECANE" condensed "SOLIDDECANE";
How to define a wax model

There is a choice of wax models since the introduction of the Coutinho model,
described in Modelling wax deposition on page 41.
Although, in principle the multisolid model can be based on any of the cubic
equations of state to model the fluid phases by users writing their own model
description the default option uses RKSA as the fluid phase model. Parameters
for the wax model have been optimised with RKSA as the liquid phase model.
However, for users who wish to use PRA as the fluid model we have retained the
waxpra.mfc file.
The wax model may be specified interactively or by loading the wax model
configuration file, waxrksa.mfc (for the multisolid model) or waxcouth.mfc (for
the Coutinho model). Either may be included in a problem setup file.
To define the wax model in Windows interactive program:
Click the Waxes tab to activate the waxes dialog box.

A message box will indicate that the model has been successfully defined.
How to define the asphaltene model

The asphaltene model is defined in the same way as equations of state or the
hydrate model, select the Asphaltenes tab in Select Model Set , click on Define
Model and you will see a message box to say the model has been successfully
defined. This will be reflected in the main window. For more information on
how to make best use of the asphaltene model see Case studies Asphaltene
flocculation on page 211.
Combined Solids Model

In earlier versions of Multiflash a user could append the multisolid wax model to
a fluid phase or solid model, such as hydrates or asphaltenes. This allowed users
to determine, for any flash condition, whether wax and hydrate (or wax and
asphaltene) could form and how the presence of one solid might affect the
formation of the other. In later versions we have a new tab, Combined Solids

The new tab allows you to specify any combination of wax, hydrate and
asphaltene solid phases. To avoid over complication specific models have been
chosen for each of the phases, based on what we believe to be the best option.
The fluid phase model is RKSA, as this is basis of tuned parameters for the other
solid phases. The salt model is based on the Electrolyte approach. The wax
model is Coutinho and there is currently only one choice of asphaltene model.
If you define only one type of solid you will be asked to use the individual solid
model tab.
Troubleshooting - models
We have tested the Multiflash software as far as is possible and corrected any
errors we have found, if you find any we havent please report them to us.
However, there is also a category of problems which we have run into ourselves
which can usually be resolved by the user. Some of those related to models are
discussed below, others will be outlined in the relevant section.
Incorrect path
All the problem setup files and model configuration files will be copied to the
installation directory. However, it is possible that you will wish to create a
working directory containing your own problem files, which is different from the
program installation directory. In this case you should copy the .mfc files into
your working directory or always refer to any .mfc files using the full path name.
For example, the sample file C4C5a.mfl contains the command
include pr.mfc
which should read in the contents of the pr.mfc file. If the pr.mfc file is not in
the same directory as C4C5a.mfl then you will see a message of the type

where the pathname refers to your working directory,
and the message in the main window will be:
remove all;
include pr.mfc
*** ERROR 402 ***
Cannot open this file.
If the installation directory was c:\MF then the correct command would be,
include "c:\MF\pr.mfc";
You should either change the .mfl file or copy the .mfc files to the designated
directory to correct the problem.
Model is not licensed

You may not have licensed all the possible model options. The standard
Multiflash licence includes equations of state and activity models, but not the
CSMA, PC-SAFT, hydrate, wax or asphaltene models, which are separate
options. The models which are not available will be disabled.
Groups not available for UNIFAC model

The UNIFAC model generates the binary interaction coefficients from group
contributions. Although the majority of components in both the INFODATA
and DIPPR databanks can be constructed from UNIFAC groups this is not
possible for all components. The light gases and refrigerants are typical
examples. If this is the case then you will see a warning message
and in the main window

*** WARNING -11742 ***One or more components have
no UNIFAC group structure
However, if you define the model first this warning message will not be
generated until you have defined components and tried to carry out a calculation.
If you do encounter a situation where UNIFAC groups are missing,
particularly for light gases, you should try loading the PSRK
model. PSRK is a variant of UNIFAC with additional structural
groups.
If there are missing groups then you should note that because UNIFAC is the
liquid phase model, if you try to carry out flashes involving the liquid phase, e.g.
dew and bubble point, calculations the flash will fail. However, the gas phase

for the UNIFAC VLE model set is defined with a separate gas phase model and
isothermal flashes will apparently work with the stream being reported as all gas.
Binary interaction parameters

Binary interaction parameters (BIPs) are adjustable factors which are used to
alter the predictions from a model until these reproduce as closely as possible the
experimental data. BIPs are usually generated by fitting experimental VLE or
LLE data to the model in question, with the exception of UNIFAC, LCVM and
PSRK BIPs which are predicted by group contribution. BIPs apply between pairs
of components. However, the fitting procedure may be based on both binary and
multi-component phase equilibria information, the former being the most
common.
Number of BIPs related to any model

Different models require differing numbers of BIPs and these may or may not
have physical significance. The cubic equations of state (RK, RKS, PR) require
only a single BIP. The closer the binary system is to ideality the smaller the size
of the BIP which will be zero for ideal systems. It is unlikely that the value of
the BIP will be greater than 1, although it is possible for it to be negative. For
LKP the default value of the interaction parmeter is 1.
When non-standard mixing rules are used, e.g. when using RKSA(Infochem),
then the number of BIPs increases. For the Gibbs excess energy type mixing
rules (MHV2-type and Huron-Vidal-type) the number of BIPs will be
determined by the activity coefficient model used to describe the liquid phase.
For the Infochem mixing rule 3 BIPs are needed.
PC-SAFT requires two symmetric BIPs, in addition to the pure component
model parameters. The default value for both is zero.
The Wilson A and UNIQUAC models require two BIPs; Wilson E needs the
same number of BIPs, but these are not interchangeable with Wilson A. NRTL
needs two binary energy interaction parameters and a non-randomness factor,
. With the exception of , these BIPs may take a wide range of numerical
values and more that one set may adequately represent the same experimental
data. The BIPs for the activity models are asymmetric and it is important to
define the binary pair of components i and j in the correct order to agree with
the fitted or reported BIPs.
The NRTL parameter defaults to 0.3 for VLE calculations and 0.2 for LLE
calculations. Values derived from fitting to experimental data will vary but are
unlikely to be much greater than 0.6.
The Regular Solution and Flory Huggins models both use the same bipset; the
BIP is symmetrical, dimensionless and the default value is zero.
Units for BIPs

The BIPs for equation of state methods are dimensionless. For some of the
activity coefficient models they are dimensioned with the exception of Wilson
A, Regular Solotuion and Flory Huggins. The dimensions used in Multiflash are
J/mole and if BIPs from external sources are used in Multiflash it is important
that they match Multiflash conventions in terms of model definition and units.

Temperature dependence of BIPs
In most of the open literature sources the reported binary interaction parameters
will be temperature independent, i.e. constants. However, Multiflash allows for
any BIP to be temperature dependent with either a linear or a quadratic
dependence, although we do not recommend this for the NRTL parameter.
BIPs available in Multiflash

Our main BIP bank is applicable to oil and gas processing operations and called
appropriately, OILANDGAS. This contains BIPs for the cubic equation of state
models PR, PRA. RKS, RKSA and RKSA (Infochem) for hydrocarbons, water,
methanol, glycols, H2S, CO2 and N2, and for the CPA model except for DEG
and TEG. The correlations have been extended to include BIPs for the LKP
model for hydrocarbon and light gas mixtures. Multiflash also provides methods
for estimating BIPs for the PR, RKS and CPA equations for mixtures that
include petroleum fractions.
The INFOBIPS BIP bank includes BIPs for the WilsonE and the VLE variants of
NRTL and UNIQUAC, based on the data reported in the Dechema Chemistry
Data Series. Some BIPs are also available for equations of state such as BWRS,
LKP and the cubics for systems not covered by the normal correlations, e.g.
binaries including ammonia. More systems will be added in future. A BIP bank,
INFOLLBIPS, stores BIPs for use with the LLE variants of NRTL and
UNIQUAC.
For the UNIFAC model , BIPs are predicted from group contributions. The data
records for pure components in the INFODATA databank contain information
on UNIFAC groups, where applicable, enabling the BIPs to be generated.
Groups for use with the PSRK and Dortmund Modified UNIFAC models are
also stored as part of the pure component UNIFAC record. Where the groups
vary, Multiflash applies the correct group structure to match the chosen model.
We have created an Infochem version of DIPPR which includes the same group
information. You will see a warning message if the group contributions are
missing for any chosen component.
It is possible to have two BIP banks in force for any problem. All the .mfc
model descriptions for the equations of state define both INFOBIPS and
OILANDGAS. When the model is defined Multiflash will first search
INFOBIPS for any specific binary BIPS, then define BIPs from the correlations
in OILANDGAS and if any are still missing they will be set to default values.
The VLE variants of the activity methods only access INFOBIPS, but the LLE
variants access INFOLLBIPS, followed by INFOBIPS.
Between releases of Multiflash we may amend, or add to, the BIPs stored. For
the OILANDGAS databank we will supply a copy of the previous banks in order
to maintain backward compatibility. The current version will still be known as
OILANDGAS4, and also the default, OILANDGAS. Previous versions such as
OILANDGAS3 can be recalled if you wish, for details on how to do this see
Supplementing or overwriting BIPs on page 56. For INFOBIPS we intend
only to issue the latest version, if users wish to maintain access to earlier
versions they should retain a copy of the relevant file.
Viewing BIP values

You can look at the values of any BIPs used in Multiflash calculations, including
those from the OILANDGAS databank and any supplied by the user. To do this
Load a problem setup file
or
Define your model and mixture

Select BIPs from Tools option in the menu bar. A dialog box for Show BIP
Values will be generated. From there you can easily view or edit any BIP values
and temperature dependence of BIPs. The BIPs values can be reported on the
results screen by clicking on the Write to Output button.
To take a particular example:
Using Select/Component from the menu, select water and decane from
INFODATA.
Specify a model. Initially define the RKS model using the Select Model
dialogue box.
Select Tools
Select BIPs and click on it The show BIP values dialog box is activated.
Select a BIP set in the dialog box.

Click edit to view or change BIP values and temperature dependence of BIPs.
Click on Write to Output button, the output will be shown in the results
window:
show bipset RKSBIP;
BIPSET: RKSBIP
COMPS ORDER VALUES
1 2 0 .50558
The output includes the name of the BIP set. The Infochem convention is to use
the name of the model followed by BIP, e.g. RKSBIP, PRBIP, RKSABIP,
RKSABIP3 (for RKSA + Infochem mixing rule ), LKPBIP, WILSONBIP2,
NRTLBIP3, UNIQUACBIP2. If the BIP name is followed by a digit, this
indicates the number of BIPs for the model or no digit means that there is only
one BIP for the model. For the CPA model the bipset name is ASSOCBIP,
while the PC-SAFT BIPs are designated by SAFTBIP and SAFTBIP-2. Regualr
Solution and Flory Huggins BIPs are named REGULARBIP. If you define your
own problem setup file you can name the BIP set as you wish.
The components are referred to by the number they are assigned in Multiflash,
i.e. the order in which they were listed in the components list.

The order is the degree of the temperature dependence of the BIP. 0 means it is
temperature independent, i.e. constant, 1 that it has linear temperature
dependence and 2 that it has quadratic temperature dependence.
If you replace decane with methanol and re-define the model to be RKSA
(Infochem) which has a non-standard mixing rule the BIP display will be more
complicated. The use of an NRTL type mixing rule means this model requires
two asymmetric parameters and one symmetric parameter.
In this case the water methanol asymmetric parameters have also been fitted with
linear temperature dependence.
If you are using defined model sets or model configuration files then there will
only be one set of BIPs for any problem. If you define a model set using two
different models e.g. an equation of state in the vapour phase and an activity
model in the liquid phase you may have two BIP datasets, one for each model.
In this case highlight the BIP dataset of interest and click on Write to Output.
The BIPs for that model will appear in the results window.
Supplementing or overwriting BIPs

If you have interaction parameters available and wish to supplement or overwrite
those stored in Multiflash you can do this using Tools/BIPs from the menu.
However, you must make sure that the BIPs you supply conform to the model
definition used in Multiflash and, for activity models, are in the correct units.
Once the BIPset is displayed, as shown above, you can type your own BIP
values into the appropriate cell to overwrite stored values.

To take a simple example, load the C4C5.mfl file used for the simple tutorial
Using Tools/ BIPs you can see that for the Peng-Robinson model the BIP for
butane/pentane is set to zero. Given the nature of the mixture this is not
surprising. However, you can enter a BIP and see the effect on the calculated
results.
If you enter a value of 0.1 you can see that the calculated bubble point
temperature at 10 bar has been reduced from 376.4K to 364.3K.
In the grid of BIPs you will notice that the symmetric BIP is displayed twice.
You need only edit one of the cells, Multiflash will automatically enter this value
in the other cell once you click on OK.
You can save your new BIPs for the current case by saving the problem setup
file. If, for certain binary pairs, you wish to overwrite the Infochem supplied
BIPs every time you run Multiflash you may wish to store these in a separate
input file. You can create this file using the BIPset table or write the file with a
text editor using standard commands. You should refer to the Appendix -
Multiflash Commands on page 253. You should refer to the Appendix in the
printed User Guide for these. The default names for the model bipsets are the
model name followed by BIP e.g. WILSONBIP2 and the number of BIPs if the
number of BIPs is greater than 1.
A typical file of BIP data might be:
bipset PRBIP 1 constant butane pentane 0.01;
bipset PRBIP 1 constant pentane hexane 0.01;
bipset PRBIP 1 constant hexane heptane 0.01;
Alternatively you might wish to create a file containing BIPs for a single binary
pair but for various models. For example for our acetone water phase equilibria
case study, see Polar systems on page 179.
If your file of BIPs contains a range of binary pairs, some of which contain
components not in your current stream you will see a warning message for each
such pair:
*** WARNING -223 ***
One or more components in this BIP set are not
currently defined
but where the components are in the stream the new BIPs will be loaded and
included in any subsequent calculations.
You should note that if you change the model your input file of BIPs will be
overwritten by the standard OILANDGAS databank included in the model
definition and you will need to reload you BIP file.
If you wish to replace the current OILANDGAS databank with a previous
version, for instance to reproduce earlier results, this is done using the

Tools/Command function. You first delete the bipset for your model and then
replace the databank, e.g.
bipset RKSABIP3 erase;
bipdata oilandgas3;
will reinstate the BIP databank issued with versions 2.7 and 2.8.
You can check which BIP banks are in force using the Tools/Show/BIP databank
option.
Troubleshooting - BIPs
The methods of displaying and editing BIPs should limit the problems you are
likely to encounter. There remain two possibilities:
Units
Reference: We cannot stress often enough that to obtain correct results the BIPs entered
Dechema Chemistry Data must match the Multiflash definition and be in the correct units. A very good
Series (CDS) source of phase equilibrium data and BIPs is the Dechema Chemical Data Series
ISSN 0840-9645 which is in several volumes. It is useful to note that their standard convention is
Volume I to XVI to report activity model BIPs for VLE in cal/mole, which need to be converted
Publisher: Dechema to J/mol for use in Multiflash. The LLE BIPs for UNIQUAC and NRTL need to
be multiplied by the gas constant R (8.314 JK-1mol-1) for use in Multiflash.
Order of components
Equations of state with standard mixing rules usually have a single symmetric
BIP. However, activity coefficient models have two asymmetric BIPs. It is
important that you enter both asymmetric BIPs and in the correct cells so that
the binary pair is consistent with BIPs supplied.
If you do not use the Multiflash BIPset grid but use commands, either via an
input file or Tools/Command then the following problems may occur.
Number of BIPs for the model

When you are supplying BIPs it is important that you define and supply the
correct number of BIPs.
Wilson A, Wilson E and UNIQUAC require 2 BIPs. If you only specify 1 after
the bipset name a warning message will appear;
Model has the wrong no. of BIPs for the existing
set
A similar message will appear if you only specify 2 BIPs for NRTL which
requires 3.
The other possibility is that you specify the correct number of BIPs for the
model, but fail to supply them all. The result will depend on the model and the
default BIPs set.
In some cases there is a generic default. If you specify NRTL with 3 BIPs and
only supply 2 the default is to set the third parameter to 0.3, for NRTL VLE and
to 0.2 for NRTL LLE. The next default level is to set the missing BIPs using
internal databanks. Finally, the default is to set the BIP to an internal model-
dependent default value.
If you specify UNIQUACBIP to have 2 constant BIPs and supply only one BIP
value before the end marker, the second BIP will be set to 0.0, and no warning

message will be issued. We recommend that you always check your supplied
BIPs using the Tools/BIPs option.
Naming the components

If you forget to enter the component names for a binary pair before the BIP
values you will upset the sequence of the command and the likely error message
will be
unrecognised keyword
BIP databank
The name of the main BIP databank for equations of state is OILANDGAS and
this is the name included in all relevant model sets and .mfc files. However,
when you save a problem set-up the .mfl file will include the full name of the
BIP bank used at the time. For Multiflash versions 2.4 and 2.5 this is
OILANDGAS2, for version 2.6, 2.7 and 2.8 it is OILANDGAS3 and for 2.9,
3.0, 3.1, 3.2 and 3.3, OILANDGAS4. If you wish to update earlier input files
you can edit them using a text editor or change the BIP bank as described above,
Supplementing or overwriting BIPs on page 78.
For WilsonE, NRTL, UNIQUAC and refrig.mfc the default databanks are
INFOBIPS (VLE variants) or INFOLLBIPS (LLE variants).
BIPs not displayed

This should no longer occur as we have increased the number of BIPs which can
be displayed. If you do still encounter problems please let us know. In the
unlikely eventuality that a particular BIP is important to you and is not displayed
you can set up a new problem file containing only the pair/pairs of components
of interest and display the BIPs for this smaller dataset.

Components
Introduction
Multiflash recognises three types of component. Normal components are pure
compounds such as hydrocarbons, petrochemicals and chemicals which may
exist as gas, liquid or solid depending on conditions of temperature and pressure.
A petroleum fraction is a pseudocomponent, usually a complex mixture of
hydrocarbons, whose aggregate properties are characterised by standard tests, the
results of which may be found in PVT laboratory reports. Finally, a condensed
component is a pure solid phase, in Multiflash these are used in chemical
equilibrium calculations only.
The physical properties for each type of component are stored or defined
differently.
Normal components
The physical properties of normal components are usually stored in databanks.
Multiflash offers two, INFODATA and DIPPRTM. INFODATA is the Infochem
fluids databank which contains data on about 200 compounds and is always
supplied as part of Multiflash. DIPPR, produced under the auspices of AIChE,
currently has data for over 1600 compounds, but is extended annually. DIPPR is
offered as an optional module for Multiflash. For details of how to find a list of
components or to search for a specific compound see Selecting components on
page 65.
Properties of normal components

Both INFODATA and DIPPR store data for each variable property (e.g. vapour
pressure, liquid density) of a component as a function of temperature. Properties
which are not temperature dependent are stored as constant values. A list of the
properties available in DIPPR and INFODATA is shown below. Some
properties may be missing for individual components.
Constant properties
Molecular Weight
Critical Temperature
Critical Pressure
Critical Volume
Critical Compressibility Factor
Melting Point
Triple Point Temperature
Triple Point Pressure
Normal Boiling Point (at 1 atm)
Liquid Molar Volume at 298.15K
User Guide for Multiflash for Windows Components 61

Standard Ideal Gas Enthalpy of
Formation at 298.15K
Standard Ideal Gas Gibbs Energy of
Formation at 298.15K
Standard Ideal Gas Entropy at 298.15K
Enthalpy of Fusion at Melting Point
Entropy of Fusion at Melting Point
Heat capacity change on fusion
Volume change on fusion
Standard Net Enthalpy of Combustion at 298.15K
Acentric Factor
Radius of Gyration
Parachor
Solubility Parameter at 298.15K
Dipole Moment
van der Waals Volume (UNIQUAC r)
van der Waals Area (UNIQUAC q)
Refractive Index
Flash Point
Lower Flammability Limit
Upper Flammability Limit
Autoignition Temperature
plus some model specific parameters. An additional parameter ACENT2 was

added in Multiflash 3.2. This is applicable only to Petroleum fractions and
allows a more accurate representation of the saturation line. No value will be
assigned for databank components.
In addition there is a group of properties that allow uniques identificationof the
name and type of the component. These are
TYPE
CAS number
FORMULA
FAMILY code
Normal databank components will be TYPE 1, petroleum fractions will normally
be TYPE 12.
Temperature Dependent Properties

Solid Density
Liquid density
Vapour Pressure
Enthalpy of vaporisation
Solid Heat Capacity
Liquid Heat Capacity
Ideal Gas Heat Capacity
Second Virial Coefficient
Liquid Viscosity
Vapour Viscosity
Liquid Thermal Conductivity
Vapour Thermal Conductivity
Surface tension
Both databanks, in addition to the properties above, also contain the UNIFAC or
PSRK group structures, where applicable. For some components coefficients
will also be stored for the second virial coeficient and realtive permittivity, both
used for model calculations.
62 Components User Guide for Multiflash for Windows

For temperature dependent properties both databanks contain information on the
upper and lower temperature limits for the correlation used for each component.
Extrapolation routines are included in Multiflash so that pure component
properties from either bank behave sensibly beyond the temperature limits of the
stored correlation.
INFODATA contains only a limited range of components, about 200, mainly
suitable for oil and gas processing. Although every effort has been made to
ensure that the data stored are correct we do not offer INFODATA as a quality
assured databank.
DIPPR is developed under the auspices of the American Institute of Chemical
Engineers. The databank contains a broad range of components including
hydrocarbons, petrochemicals, chemicals and some metals. The correlations
used in Multiflash are the recommended set for each property and component.
Questions concerning quality codes and sources of data for the DIPPR databank
should be referred to Infochem.
Condensed components
The INFOCOND databank includes about 140 solid compounds. The data are
limited to molecular weight, normal melting point, normal boiling point, the
enthalpy of formation in the condensed state at 298.15K, the standard entropy in
the condensed state at 298.15K and the heat capacity in the condensed state as a
function of temperature. It is intended for use with Infochem's chemical and
phase equilibrium module, Chemreact.
Petroleum fractions
Petroleum fractions are discussed in detail in Petroleum fractions on page 109.
To define a single petroleum fraction the program requires certain characteristic
properties and Multiflash will then estimate the other properties needed to
support the range of calculations available in the program.
The list of possible properties to support characterisation of the fraction are:
Carbon number
Molecular weight (g/mol)
Specific gravity at 60oF relative to water at 60oF
Normal boiling point
Critical temperature
Critical pressure
Pitzers acentric factor
However, not all of these are necessary. The minimum input sets are molecular
weight, molecular weight and specific gravity; molecular weight and boiling
point; boiling point and specific gravity; critical temperature, critical pressure
and acentric factor. Alternatively the boiling point can be used instead of the
acentric factor.
This input data can be supplied by the user for each fraction or provided on the
basis of a specified carbon number only. This is described in Defining
petroleum fractions on page 109.
The properties which are estimated, if they have not been provided, are:
Carbon number
Molecular weight

Critical pressure
Critical volume
Acentric factor
Parachor
Dipole moment
Enthalpy of formation
Standard entropy
Perfect gas Cp
Saturated liquid density
Saturated vapour pressure
Enthalpy of evaporation
Liquid viscosity
Defining a mixture (stream) in Multiflash

Multiflash calculates the properties of one stream (defined mixture) at a time.
Most users of the interactive program will only be using a single stream
throughout their calculations. However, a more recent option is the ability to
define stream types, subsets of the original stream which contain only a defined
sub-set of the original components. However, each stream type can be defined
by a different model. For more information see Stream types on page 76.
The original stream can be defined in two ways, either through the Select
Components route or via the PVT Lab Fluid Analysis.
Using Select Components the stream is defined by first choosing the data source;
the databank which will be used to generate the pure component physical
properties and then choosing which components in the mixture you wish to be
taken from that source. More than one source can be used to define the stream.
A common problem in oil and gas processing might require a choice of
hydrocarbons from INFODATA and several petroleum fractions defined using
the petroleum fraction correlations.
Alternatively, some users may wish to define the stream using the fluid analysis
report they have received from a PVT laboratory. Typically the fluid analysis
will comprise a series of defined pure components (discrete components) and a
series of pseudo components. The method of doing this is described in detail in
Petroleum fractions on page 109.
The maximum number of components in any mixture in the
current version of Multiflash is 100.
Defining the pure components in a stream will be discussed below.
Specifying the data source

To define the data source first
Select Select from the menu bar, then
Select Components
or click on the select components button, .

Either will activate the Select Components dialogue box.

with the Infochem fluids databank showing under data source as the default
databank. To choose any of the other data sources click on the button to the
right of data source. Select the chosen databank and this will appear in the data
source text box.
Selecting components
If the specified data source is a databank, e.g. INFODATA or DIPPR, then the
components for any stream can be selected in a variety of ways depending on
your knowledge of the contents of the databank and the name or synonym by
which your chosen component is listed in the bank. If you are uncertain about
any of these then there are various search strategies in place to help you find the
components you need.
Select components by scrolling through a list

Choose the All Components option button and a list of the standard bank
names for the compounds stored in the chosen data source will appear. You can
then scroll through the list until you see a component you require. This is quite
convenient for INFODATA but may take a long time for a large databank like
DIPPR.

The component is then selected for use in Multiflash either by double
clicking on the name or by selecting the name, which will then be
highlighted and then clicking on the Add button. The name of the selected
compound will then appear in the Components selected in Multiflash text box.
Further components may be selected the same way.
Select components by name

If you know the name or synonym under which a component is stored then
firstly ensure the Name option button is selected, then type the name of the
component in the text box. The name may be entered in upper or lower case.
The component will be transferred to the selected set by pressing the enter
key after the name or by clicking on the Add button.
If you are not certain whether a particular name in the databank list represents
the component of interest to you, or if are not sure that you have the correct
name for a component, you may wish to check the other names (synonyms)
stored in the bank for that compound.
Synonyms
To check the list of synonyms stored in a data source for any component type
the name in the Enter name text box, make sure the Synonyms option button is
selected and click on the Search button

The list of synonyms stored for this component will be displayed. If this proves
to be the component you wanted you can then select the synonym to be used in
the Multiflash output to identify the component by selecting it in the normal way
(double clicking on the name or highlighting the name with a single click and
using the Add button). In the list used to illustrate this facility we have chosen
the DIPPR databank. One of the synonyms available is the DIPPR databank
number for the component, in this case 1201. The last synonym in the list is
000107-21-1, which is the Chemical Abstracts registry number.
Select components by formula

You may only know the formula of the component you wish to select. In this
case select the Formula option button and type the formula in the text box.
Compounds with matching formulas will be displayed and may be selected in
the usual way.
It is important that the formula is defined in terms of standard chemical symbols,

e.g. C6H10O, not c6h10o.
Neither of the compounds corresponding to the chosen formula are in
INFODATA, if you replace DIPPR with INFODATA as the data source and
repeat the search the you will see the following warning. This also contains a

reminder of the correct nomenclature for the formula in case this was the source
of the problem.
You can also search the databanks using a partial formula. In the current version
of the program you may replace the number of any of the atoms in a component
by a *, but you must name all the different atoms in the compound you are
searching for. For example, C2Cl*H* will find all ethanes that contain chlorine.
Select components by substring

You may wish to search the bank using only a portion of the name: perhaps you
are interested in seeing which components contain a certain subgroup. Select the
Substring button and type the portion of the name which identifies the group of
interest in the text box. You can specify whether the string is to be at the start of
a name, at the end of a name or anywhere in a name using the * character. For
example methane* finds all names starting with methane; *methane finds all
names ending in methane and *methane* finds all names containing methane.
Entering methane alone searches for an exact match.
Adding, inserting, replacing and deleting

components
You may add additional components to an existing mixture, replace components
or delete them. You can add a component into an existing mixture at any given
point in the selected list using the insert command.
Adding a component
Components are added to the selected list for a mixture as described earlier, by:
Double clicking on a component in a list.
By pressing the enter key after entering a name in the text box
(with Name option button selected).

By selecting the compound from a list and clicking on the Add
button.
If you try to add the same component twice you will be warned
and the action will not be allowed.
Inserting a component
If you want to add a component to the selected list, but in a particular position,
perhaps so that the compounds are in order of carbon number in the program
output, then:
Select the compound as usual by entering the name or highlighting it in a list
Highlight (by clicking on it) the compound in the Multiflash list above which
you wish to insert the new component
Click on the insert button.
Deleting a component
If you wish to remove a component from the selected list then, in the
Compounds selected in Multiflash text box:
Select the component, then
Click on the Delete button
The compound will then be removed from the list.
Replacing a component
If you wish to replace one component with another you can do this without first
deleting it from the selected list.
Select the component to be replaced
Select the new component (either by typing in the name or using one of the
other selection methods)
Click on Replace.
The new component replaces the highlighted component.
Note that when you replace an existing component the amount
of the new component in the mixture remains the same as the
amount of the component it replaced unless you change the
composition in the Composition drop down table.
Viewing and editing pure component data.

If you wish to obtain the values of any property for a pure component at specific
conditions then you should consult the case study shown in Case studies - Pure
component data on page 173. in the printed User Guide. If, however, you want
to look at the stored data record for any component in the mixture then this can
be done by using the Tools/Pure Component Data menu option. The
components in your stream will be displayed in a subsidiary window together
with a list of stored properties.

Highlight the component of interest and the property or group of properties
required, click on Edit and the relevant section of the data record will be
displayed.
For constants the individual property values will be shown:
whilst for temperature dependent properties the coefficients of the correlation

equation will be displayed.

Any of these data may be overwritten by typing the new value in the appropriate
cell in the correct units. These may be changed using the Units button. You can
also use this Edit facility to change the name of the component for the duration
of any calculations.
The data record can also be displayed in the main window using the Write to
Output button.
User-defined components
We do allow you to add user-defined pure component data, for instance when the
component you require is not available in our databanks. From the Data Source
select User-defined component from the drop-down list, then give the
component name in the text box and press Enter.
The physical properties for this component will be specified using the
Tools/Pure component Data option in Multiflash main window. Return to the
main window and activate this option, selecting your user-defined component
and the Edit option, choosing to edit Constants initially. The Pure component
data bank will appear with the Value column empty.

To define your component simply enter the value for the listed property,
ensuring that you use the correct units, e.g.
To enter a temperature dependent property, such as the ideal heat capacity,

choose the property keyword (in this case CPIDEAL) and click on Edit, or
double click on CPIDEAL. A form will be displayed defining the component
name and property but with the remaining text boxes blank.

As soon as you enter the Equation number the correct number of cells for the
coefficients of this equation will be displayed and you enter the values of the
coefficients. The temperature limits for your correlation should also be entered.
The equation types available for each property are set out in the Multiflash
Command Reference Manual, together with a description of each equation and
the number and order of the coefficients. All equations are specified as a
function of temperature in Kelvin and you should only enter coefficients which
have been fitted in Kelvin. Click on OK to define the property.
The minimum data required to perform any phase equilibrium calculation with
Multiflash using the basic equations of state are critical temperature, critical
pressure and acentric factor for each component. The data requirements are
model dependent and models other than the equations of state require additional

data. Isenthalpic and isentropic calculations also require coefficients for the
ideal-gas heat capacity for each component. To work in mass units rather than in
molar units the molecular weight is needed.
The minimum requirements for phase equilibrium and transport property
calculations for the models available in Multiflash are given in the following
Table.
Model Minimum input

Thermodynamic
RKS critical temperature (TCRIT), critical pressure
(PCRIT), acentric factor (ACENTRICFACTOR),
ideal gas Cp (CPIDEAL)
RKSAPI critical temperature (TCRIT), critical pressure
RKSA critical temperature (TCRIT), critical pressure
vapour pressure (PSAT), saturated liquid density
(LDENS), ideal gas Cp (CPIDEAL)
RKSAINFO critical temperature (TCRIT), critical pressure
PR critical temperature (TCRIT), critical pressure
PRA critical temperature (TCRIT), critical pressure
PSRK critical temperature (TCRIT), critical pressure
(LDENS), ideal gas Cp (CPIDEAL) ), UNIFAC
subgroup structures (UNIFAC)
LCVM critical temperature (TCRIT), critical pressure
(LDENS), ideal gas Cp (CPIDEAL) ), UNIFAC
subgroup structures (UNIFAC)
LKP critical temperature (TCRIT), critical pressure
BWRS critical temperature (TCRIT), critical pressure
(PCRIT), critical volume (VCRIT) and acentric
factor (ACENTRICFACTOR) for components
not in model database, ideal gas Cp (CPIDEAL)
CSM critical temperature (TCRIT), critical pressure
(PCRIT), critical volume (VCRIT), ideal gas Cp
(CPIDEAL)
CPA critical temperature (TCRIT), critical pressure
(LDENS), association parameters (ASSBE,
ASSEP, ASSGA), ideal gas Cp (CPIDEAL)
PC-SAFT critical temperature (TCRIT), critical pressure
PC-SAFT parameters (SAFTEK, SAFTSIGMA,

SAFTM, SAFTKAPPA, SAFTEPSILON,
SAFTFF), ideal gas Cp (CPIDEAL).
Note (1) TCRIT, PCRIT and
ACENTRICFACTOR are necessary to generate
starting values for flash calculations but do not
affect the computed results from PC-SAFT. (2)
SAFTKAPPA, SAFTEPSILON and SAFTFF are
only needed for associating components.
Ideal solution vapour pressure (PSAT), saturated liquid density

(LDENS)
NRTL vapour pressure (PSAT), saturated liquid density
(LDENS)
Wilson E vapour pressure (PSAT), saturated liquid density
(LDENS)
UNIQUAC vapour pressure (PSAT), saturated liquid density
(LDENS), surface and volume parameters
(UNIQQ, UNIQR)
UNIFAC vapour pressure (PSAT), saturated liquid density
(LDENS), UNIFAC subgroup structures
(UNIFAC)
Dortmund Modified vapour pressure (PSAT), saturated liquid density
UNIFAC (LDENS), UNIFAC subgroup structures
(UNIFAC)
Regular Solution vapour pressure (PSAT), saturated liquid density
(LDENS), solubility parameter (SOLUPAR) and
molar volume at 25C (V25).
Flory-Huggins vapour pressure (PSAT), saturated liquid density
(LDENS), solubility parameter (SOLUPAR) and
molar volume at 25C (V25).
Ideal gas ideal gas Cp (CPIDEAL)
RK critical temperature (TCRIT), critical pressure
(PCRIT), ideal gas Cp (CPIDEAL)
Hayden OConnell critical temperature (TCRIT), critical pressure
(PCRIT), radius of gyration (RADGYR), dipole
moment (DIPOLEMOMENT), Hayden-
OConnell association parameter (HOCASS),
Freeze-out melting point (TMELT), enthalpy of fusion

(HMELT), heat capacity change on fusion
(CPMELT), volume of fusion (VMELT)
Hydrate potential parameters (HYD1, HYD2, HYD3),
cavity occupation code (HYDOC)
Wax melting point (TMELT), enthalpy of fusion
(HMELT), heat capacity change on fusion
(CPMELT), volume of fusion (VMELT)
Asphaltene critical temperature (TCRIT), critical pressure
(LDENS),
Transport properties
Pedersen critical temperature (TCRIT), critical pressure

(PCRIT), molecular weight
(MOLECULARWEIGHT)
Twu molecular weight (MOLECULARWEIGHT),
boiling point (TBOIL), vapour pressure (PSAT),
saturated liquid density (LDENS)

LBC critical temperature (TCRIT), critical pressure
Lohrentz-Bray-Clarke (PCRIT), critical volume (VCRIT), dipole
moment (DIPOLEMOMENT), molecular weight
(MOLECULARWEIGHT)
CLS critical temperature (TCRIT), critical volume
Chung-Lee-Starling (VCRIT), dipole moment (DIPOLEMOMENT),
molecular weight (MOLECULARWEIGHT)
Macleod-Sugden parachor (PARACHOR)
Costald critical temperature (TCRIT), critical pressure
saturated liquid density (LDENS)
Liquid viscosity mixing liquid viscosity (LVISC)
rule
Vapour viscosity mixing vapour viscosity (VVISC)
rule
Liquid thermal liquid thermal conductivity (LTHCOND)
conductivity mixing rule
Vapour thermal vapour thermal conductivity (VTHCOND)
conductivity mixing rule
Surface tension mixing surface tension (STENSION)
rule
Diffusivity Fuller's molecular weight (MOLECULARWEIGHT),
method chemical formula (FORMULA), UNIFAC
subgroup structures (UNIFAC).
Diffusivity - Hayduk- critical temperature (TCRIT), critical molar
Minhas method volume (VCRIT), normal boiling point (TBOIL),
parachor (PARACHOR) dipole moment
(DIPOLEMOMENT), saturated liquid density
(LDENS), chemical formula (FORMULA),
UNIFAC subgroup structures (UNIFAC).
To save the pure component data you have entered you must save the data to a
file, using File/Save Problem Setup.
Stream types
For certain applications you may wish to define one or more sub-streams formed
from selected components of your overall input stream and describe these by
different models. Typically, this will be when you are using Multiflash to define
input data for a third party application such as a simulator where the composition
of the fluid will be changing with various unit operations. As the composition
changes different models may be more appropriate for different streams. A
simple example, shown in the Multiflash Excel manual, is to describe a mainly
hydrocarbon stream containing some water and glycol using a cubic equation of
state for high and low pressure separator flashes but to change to an activity
model to look at glycol regeneration from the recombined water streams.
We will describe how to set up stream types in Multiflash for Windows.
However, in the interactive version of Multiflash the composition of a sub-
stream cannot be changed without altering the composition of the overall stream
and it is difficult to define a realistic practical application for the interactive
version.
Initially we have defined an input stream containing 4 hydrocarbons, a
petroleum fraction, water and DEG and supplied a composition.

If you then activate the stream type selection using Select\Stream Types\Define
you will be asked to define a model for your stream, in this case PRA. The
format is exactly the same as the usual Select Model Set with the same options.
Once you have clicked on Define Model, a message box will confirm that the
model has been successfully defined. Click on OK to activate the Define Stream
Type text box. If you have not defined a Model Set prior to activating the Select
Stream Type option then you may wish to choose All components and call this
your overall stream type.

If you had already chosen a model using the Select/Model Set route before
activating the Define Stream Type text box then creating an additional stream
containing All components and using the same model may be superfluous. In
addition to any new stream defined at this stage the program will also define an
"Original" stream type containing this information. Click on Define Stream
Type and on OK to define the stream. To check defined streams use the
Tools/Show/Stream types option.
show Sts;
NO. OF STREAM TYPES 1
1 OVERALL
A second stream can be defined the same way. This time we have selected the
NRTL VLE model and defined a stream called DEG containing only water and
DEG
We can check this as before

show Sts;
NO. OF STREAM TYPES 2
1 OVERALL
2 DEG
If you wish to assign BIPs for this stream you do this using Tools/BIPs, Click on
the model/BIP name for the stream and enter the values in the BIP grid.
If you try to define a further stream with the same name as a previous stream
type you will be warned that the stream exists and asked if you wish to replace it.
However, you can define a further stream with the same components and model
if you call it by another name.
To Delete a stream type choose the Select/Stream Type/Delete option, highlight
the name of the stream to be deleted and click on Delete Stream Type.

When you wish to carry out calculations relating to a particular stream, activate
that stream using Select/Stream Type/Select Active, highlight the stream you
wish to work with and Select Stream Type.
You can then carry out any Multiflash calculations using that stream with its
selected components and the composition defined in the drop down Composition
table.
Hydrate inhibitors
Some of the pure components in INFODATA act as hydrate inhibitors, see
Inhibitor modelling on page 39. The most common are methanol, MEG,
DEG, TEG and salt. Any of these can be included in the component list as
described above and their composition defined as shown in Specifying
compositions on page 127. Indeed this is the way you should specify ethanol,
isopropanol, propylene glycol and glycerol. However, for methanol, glycols and
salt you can also use the Inhibitor Calculator.
Inhibitor calculator
The Inhibitor Calculator was included to make the addition of inhibitors easier.
The Inhibitor Calculator is designed to calculate the amount of inhibitor or
inhibitors to be added to the amount of water present in the stream to reach a
user defined inhibitor concentration. This concentration may be defined in mass,
mole or volume units.

The Inhibitor Calculator can also be used to add both water and the inhibitors to
the components list. If they have not already been included they will
automatically be added to the components list along with the calculated
compositions.
To calculate the amount of methanol or glycols relevant to the amount of pure
water present in the stream first
Select Inhibitor Calculator from Tools menu bar. The tabbed dialog box for
water, alcohols and glycols will be activated.
Select a databank from which the components are defined.
If you have already defined the amount of water in the stream it will be reflected
in the dialog box. Otherwise, you must first enter the amount of water to which
the inhibitor is to be added (in the correct units) so that the boxes for methanol,
MEG, DEG and TEG can be enabled. Then specify the required concentration
in water of inhibitor or inhibitors in mass %, mole % or volume % at standard
conditions. Standard conditions are normally considered to be 1 atmosphere and
60 DegF or 15 DegC.
Click Add button. Then the equivalent amount of inhibitor relevant to the
amount of water will be added automatically to the list of compositions of the
stream.
Click Close button to return to the main window.
Note that you can calculate the amounts of any combination of the four
inhibitors to be added to water but the total percent of the inhibitors must be less
than 100.
If you are carrying out fixed phase fraction flashes with glycol inhibitors at high
concentrations (of the order of 75 wt% plus) you should allow for the possibility
of the glycol forming a solid phase. The melting points of the pure glycols are
relatively high. To do this you should set up a freeze-out model for the glycol

using the Select/Freeze-out Components option, see The Freeze-out model on
page 48.
Salt calculator
For the original salt model one of the components in the INFODATA databank
was called salt component. This is used to represent a salt pseudocomponent,
based on a sodium chloride equivalence, for use in calculating freezing point
depression or hydrate inhibition, see ( Calculations with inhibitors on page
197). For the new salt model, which is based on defining ions and not a salt
pseudocomponent, the ions Na+ and Cl- have been added to the databank. More
ions will be added in future versions.
To determine the inhibition effect of salt using either salt model you need to
provide a description of the salt content of the aqueous stream but often the data
for the salt, brine or formation/production water ion analysis will not be
available to you in the appropriate units. To help generate the data in the form
required by Multiflash we have an extended Tools/Inhibitor Calculator menu
option.
The water content of your stream can be defined from Select Components and
the Composition box or entered in the Water text box under the
Water/Alcohols/Glycols tab as described above.
Depending which salt model you wish to use you can either include the salt
component or the Na+ and Cl- ions in your component list by selecting from
INFODATA. However, an easier approach is to select either the Salt
Component Model or the Electrolyte Model tab from the Inhibitor Calculator.
With the appropriate tab selected you can define your salt from:
an Ion Analysis table
a Salt Analysis table

or the total amount of dissolved solid.
Clicking on the Add Salt button then initiates the calculation of either the
amount of salt component (Salt Component Model) or the amount of NaCl
(Electrolyte model) to be added to the stream in the units defining your
composition

The amount of either salt component or Na+ and Cl- ions will also be entered in
the Composition drop-down table.
If you try to add more salt than is physically realistic you may generate an error
message such as
You will also generate error messages if you define only negative or positive
ions in an Ion Analysis table
If you enter values on more than one analysis option the amount of salt to be
added will be taken from the table for which you activate the Add Salt button.
If you are carrying out fixed phase fraction flashes with a salt component present
in your stream and a low ratio of water to salt you should allow for the
possibility of a separate solid salt phase forming. To do this you should set up a
freeze-out model for the salt component using the Select/Freeze-out Components
option, see Solid freeze-out model on page 37.
The "Salt Component " option can only be used with the RKSA(Infochem"
hydrate model. If a salt component is present in the components list and you re-
define the model to CPA or RKSA(Infochem) + Elecrolyte options the salt
component will automatically be removed. Similarly, if the elecrolyte salt model
has been selected and Na+ and Cl- are present in the component list they will be
automatically removed on selection of the RKSA(Infochem) hydrate model.
If you wish to add both methanol and salt you enter the required concentrations
in the relevant Alcohols/Glycols and "Salt Component" or "Electrolyte" tab.
Clicking on Add in any tab will add the correct level of chosen inhibitor.
Troubleshooting - components
Despite all our efforts to test and debug the software there may be genuine errors
which should be reported to us. However, there are a range of problems,
commonly encountered, which can be rectified fairly easily. We hope the
associated warning messages are useful but if not please let us know.
Databank not found

All licensed databanks will be loaded in the installation directory. However, it is
possible that the files may have been moved or overwritten. If a databank cannot
be found then the following warning message will appear when you use the
Select Component dialogue box.

If you attempt to load a Multiflash problem file that defines the databank and the
databank cannot be found a message similar to the following will appear.
The message in the results window will be something like::

*** ERROR 12952 ***
Cannot open INFODATA format databank files.
The path used by Multiflash to find databank files is set in a configuration file
called AYCONFIG.DAT. See the separate Installation Guide for further
information. The files needed by INFODATA are identified in the
AYCONFIG.DAT file by the keywords INFODATA_PURE and
INFODATA_INDEX. For DIPPR the keywords are DIPPR_PURE and
DIPPR_INDEX. Check that the pathnames associated with these keywords are
fully defined, including the correct drive, and that the databank files exist.
If the AYCONFIG.DAT file itself is missing then Multiflash will not produce
output in the main window and none of the data sources will be accessible.
Databank not licensed

If you have not licensed DIPPR then warnings will appear which are similar to
those reported when the databank is not found on the specified path, but the only
corrective action is to substitute INFODATA as the data source or extend your
licence.
Component cannot be found

The component you need may not be stored in any of the available databanks,
although this is less likely if you have DIPPR installed.
The warning message is self-explanatory
Before you accept this, however, it is worth checking

That you have spelt the name correctly

That a formula or substring search cannot identify the component
under another name
That formula searches are specified in standard chemical
nomenclature
TIP If the component you cannot find on the databank is present only in small or
trace amounts it may be possible to substitute a similar compound without
significant error. However, this will clearly depend on the particular calculation
and application.
Too many components in the mixture

The maximum number of components in a mixture in the current version of the
software is 100. If you try to select more than this you will be warned that the
limit has been reached.
TIP If you have some components of similar type and size in your mixture,
preferably present in small amounts, then it may be worth combining them to
reduce the overall number of components. This is particularly useful when
dealing with natural gases and gas condensates which have been analysed in
great detail.

Petroleum fractions
Introduction
In the oil and gas industry a fluid may not be entirely composed of well defined
pure components. It may be composed of a combination of pure components
plus one or more pseudocomponents or petroleum fractions. Such fractions are
usually a complex mixture of hydrocarbons, whose aggregate properties are
characterised by standard tests, the results of which may be found in PVT
laboratory reports.
Defining petroleum fractions

To define a single petroleum fraction the program requires certain characteristic
properties and Multiflash will then estimate the other properties needed to
support the range of calculations available in the program.
The list of possible properties to support characterisation of the fraction are:
Carbon number
Molecular weight (g/mol)
Specific gravity at 60oF relative to water at 60oF
Critical pressure
Pitzers acentric factor
However, not all of these are necessary. The minimum input sets are
molecularweight, molecular weight and specific gravity; molecular weight and
boiling point; boiling point and specific gravity; critical temperature, critical
pressure and acentric factor. Alternatively the boiling point can be used instead
of the acentric factor.
The properties that are estimated, if they have not been provided, are:
Molecular weight
Critical pressure
Critical volume
Acentric factor
User Guide for Multiflash for Windows Petroleum fractions 87

Parachor
Dipole moment
Enthalpy of formation
Standard entropy
Perfect gas Cp
Saturated liquid density
Saturated vapour pressure
Enthalpy of evaporation
Liquid viscosity
Melting temperature
Enthalpy of fusion
Entropy of fusion
Heat capacity change on fusion
Volume change on fusion
If you have the required input properties available, either from the PVT Analysis
or from a previous characterisation (possibly from a simulation program), you
can enter these and estimate the remaining properties as described in
Calculating petroleum fraction properties on page 118.
If you have pseudo components specified by carbon number and you wish to
retain these but have no properties for them you can allocate these from the
recommendations of Riazi and Al-Sahhaf, see Defining petroleum fractions on
page 87.
However, you may also have available a compositional PVT analysis where you
need to break down one or more pseudocomponents into further fractions or
where you wish to regroup the fractions into fewer cuts.. A typical application
of extending the analysis of the heavy end of an oil would be when modelling
waxes or asphaltenes. In this case you must first characterise the fluid and the
PVT Analysis is designed to help you with this.
PVT Analysis
The PVT Lab Analysis form was designed to allow you to enter the information
supplied by PVT laboratories as quickly and easily as possible. As we actively
improve characterisation procedures the input form is modified, although the
basic structure remains the same. In Multiflash version 3.1 we provided two
forms in place of the single original. One form allowed you to enter a Single
total fluid composition, the other to mix separator gas and separator liquid
compositions.
In Multiflash 3.2 these forms were duplicated but with extended input to allow
the entry of a n-paraffin distribution. This was needed in 3.2 to support the new
Coutinho wax model. When a n-paraffin distribution is not available it can be
estimated for use with Coutinho's model and allowance is made on the Single
fluid and Liquid-Gas forms for the required input. In Multiflash version 3.3 a
fifth input form has been added for a Black Oil Analysis and the layout of the
common elements of all five forms has been modified.
88 Petroleum fractions User Guide for Multiflash for Windows

Analysis method
Our new analysis improves the way in which the fractions in a fluid are
distributed, i.e. grouping and splitting fractions and the allocation of properties.
For backward compatibility you can retain the original analysis
method(Infoanal1), based on the Whitson Gamma distribution. The new analysis
method is designated as Revised method (Infoanal2). It has the following
features:
The code is able accurately to regress the single carbon number
analysis up to very high carbon numbers if given. The Whitson
gamma function method which was used in the original method
was not able to fit actual experimentally measured distributions in
some cases.
The code will estimate the likely tail of the distribution
corresponding to the plus fraction and make use of molecular
weight data in estimating the tail. The method will function for
extremes of a single C6+ plus fraction to cases where the analysis
goes up to very high carbon numbers .
The code performs checks on user specified molecular weights and
specific gravities to ensure they are consistent with the specified
analysis.
As with the old characterisation method, the user can ensure that
all inputs are genuine measured quantities, i.e. the liquid analysis
can be specified on a mass basis, a separate gas analysis and
recombination GOR can be given and the molecular weight and
specific gravity can be specified for the stock-tank liquid.
The pseudocomponent lumping procedure uses a new method to
ensure that the lumped equation of state model will behave as
similarly as possible to the unlumped equation of state model.
Component list
A list of possible components is already provided based on a typical list from a
PVT laboratory. This consists partly of well-defined (discrete) compounds such

as nitrogen or methane and partly of pseudocomponents such as C6, C7 etc. up
to C65. These are often referred to as single carbon number (SCN) cuts. You
can choose the data source for the discrete compounds, e.g. INFODATA or
DIPPR.
However, you may use a different laboratory which provides a different list of
discrete components and you may therefore configure the list as you wish.
To delete a component simply highlight the component you wish to remove and
click on the Component Delete button to remove it from the list.
To add a component highlight the component above which you wish to add a
new compound and click on Component Insert. A blank row will be inserted.
Simply type choose the pure component datasource from which you wish to take
the data and type in the name of the new component to be added. For instance
cyclopentane has been added to the list below.
Only hydrocarbons can be added to the component list in the PVT Analysis. If
you try to add a component such as acetone then you will see a warning message
to indicate that the component cannot be added.
If you wish to add this component to carry out phase equilibria calculations then
you should characterise your fluid without the components present, return to the
main window and then add the component using Select Components.
If a proposed new component is already in the list and the amount of the
component is left blank, then the component will be ignored and the PVT
characterisation will proceed as normal. If the component is already in the list
with a either positive or zero amount then an error message will be generated
when you try to do the characterisation.

If you mis-spell the component name or the component you wish to add is not in
the datasource of your choice another error message will be generated.
Only one datasource can be active when carrying out PVT characterisation. This
means that if the component you wish to add is only available in DIPPR (if you
have licensed this) changing the datasource from Infodata to DIPPR will also
change the source of pure component properties for all the discrete components.
If you wish the component list of your choice to be generated automatically you
can do this by adding the PVT Analysis component list to your MFCONFIG.dat
file. The easiest way to do this is to set up the list as you want it in Windows
and then use Tool\Show problem to reflect the changes in the main window.
Highlight the commands defining the pvtanalysis then copy and paste this to
your mfconfig.dat file. The next time you run Multiflash and use the PVT
Analysis the new component list will be generated automatically.

Fluid composition
How you enter the fluid composition will depend on the information supplied by
the PVT Laboratory: this may be supplied as information on the total reservoir
fluid or as a separator fluid, separator gas and GAS to OIL ratio (GOR).
If you only have a total liquid composition this should be entered using the
Single Fluid option. If you have both gas and liquid you need to enter the fluid
compositions using the Liquid-Gas option.
The GOR is a value provided by the PVT laboratory carrying out the analysis to
allow the user to recombine the gas and liquid analyses correctly in order to
obtain the correct fluid composition for the recombined fluid. We have altered
the description of GOR in the PVT form to reflect this. In Multiflash verion 3.3
the position of the GOR box has been moved. In order to carry out a
characterisation for the Gas and Liquid analysis you must have a composition in
both columns.
Compositions can be entered in either mass or mole % by using the drop down
menu at the top of the column and different units can be chosen for gas and
liquid. However, changing from mass % to mole % once amounts have been
entered will not lead to a unit conversion, the same values will be retained but in
different units.
As amounts are entered the Total % will be summed. If the Total % does not
equal 100% you will be offered the option to normalise the percentages before
the characterisation is carried out. Although the pseudocomponents will
normally run sequentially in terms of single carbon number it is possible to have
data from a non-laboratory source where the SCNs are not sequential. You can
still enter these, leaving gaps as appropriate; if the PVT is saved or recalled zero
amounts will be allocated for SCNs where no composition was provided.
In Multiflash version 3.3 it is now possible to paste fluid compositions into the
PVT Analysis form. For example, if you recive your report from the PVT
laboratory as an Exce spreadsheet, then provided your PVT Analysis compnent
list matches (or you have altered it to match) that from the laboratory, you can
simply copy the reported composition from the spreadsheet and paste it into the
appropriate column in the PVT Analysis form.
Additional fluid information

You can provide additional information to define the fluid. This section of the
PVT Analysis form has been updated to reflect the data likely to be available.

The additional properties can be either the molecular weight of the Stock Tank
Oil (STO), the total liquid or the heaviest SCN and/or specific gravity of the
STO or the heaviest SCN. If none of these data are supplied the program will
estimate the values based on the fluid distribution you have supplied. In
previous versions of Multiflash the layout of this section apparently enabled the
user to enter the specific gravity of a total single fluid. However, as the specific
gravity was taken to be at STO conditions this could be mis-leading as a total
liquid specified might wellinclude a significant amount of light components and
would be two-phase at STO conditions. If .mfl files from earlier versions of
Multiflash, which included this specific gravity, are loaded the assumption will
be that the value referred to the STO, which is likely to be correct in most cases.
A warning message wil be triggered.
Our general advice is that if you have a lean gas, i.e. where the C6+ fraction is
only a minor proportion of the total fluid, you allow the program to estimate the
molecular weight of the heaviest SCN. For condensates and heavy oils it is
preferable to enter the molecular weight of the total fluid as this is an
experimental value. The molecular weight for the heaviest SCN shown in
analysis reports will probably have been assigned by the PVT laboratory using
generalised tables for petroleum fraction properties.
In order to give guidance when running Multiflash we have supplied some
warning messages. If the mole fraction of C6+ is <.05 and you supply a
molecular weight or specific gravity a warning message will be generated to ask
you if this is correct.
Conversely, if you have an oil where the mole fraction of C6+ is > .5 and you
fail to supply either molecular weight or specific gravity a similar warning
message will ask you to check this.

Also, if you supply a molecular weight for either the total fluid or the heaviest
SCN which does not appear compatible with the carbon number distribution you
have entered you may see either of the following warning messages:
or
If the molecular weight appears to be too large this may well be correct, you
should just check the entry. If the molecular weight appears to be too small, it is
probably because the molecular weight of the heaviest SCN is less than that
allocated to the previous SCN in the distribution. This usually indicates a
mistaken entry, but this is not always the case and the program will continue
with the characterisation should you choose to ignore the warnings.
If you have a separate gas composition this should be entered in a similar way
before doing any characterisation but you must supply the GOR (gas to oil ratio)
on a volume to volume basis. Again there is a drop down menu for the choice of
units.
n-Paraffin distribution
A n-paraffin distribution can only be entered and used with the new
characterisation procedure, Infoanal2. It applies only to the C6+ fraction , but
data entry is similar to any other PVT phase composition

The n-paraffins are part of the liquid so in this case the Total% of n-paraffins and
Other Liquid Hydrocarbons should sum to 100%. If they don't then
normalisation will adjust the Other Liquid Hydrocarbons to 100% and increase
or decrease the Total % of n-paraffins in proportion.
The boxes for starting and splitting the pseudocomponents in the n-paraffin
portion of the fluid will also be activated.
For cases where the normal paraffin distribution has not been measured, it can be
estimated. For best results, the user should specify the total wax content.
Black Oil Analysis

In some circumstances a user may have very limited compositional data for a
fluid. Either this may not have been measured or the data may have been
generated from otherapplications such as reservoir simulations. It may be that
this limited data has to be converted to a more detailed compositional aanalysis
in order to investigate other problems. The Black Oil Analysis can operate from
the minimum input data of Gas gravity(relative to air), Stock Tank Oil specific
gravity(relative to water) and Solution GOR. Additional data that may be
availabe are the Watson K factor and a Gas Analysis and these may be entered as
optional input.
The characterisation proceeds as for any other PVT Analysis data.
Wax Content
The ability to define the wax content was a new feature in the 3.2 PVT Lab
Analysis forms. The value corresponds to the values given by the UOP total wax
content test and is interpreted as giving the total C20+ n-paraffin content in the
stabilised oil.
It is a required input for the new Coutinho wax model where it is used to
calculate a n-paraffin distribution. If the wax content is unknown it too can be
estimated by ticking the box for Estimate Wax Content. If a n-paraffin
distribution is specified then the Wax Content and Estimate Wax Content boxes
are both disabled.

Water cut
In practice the fluid may also contain water. If this is pure water it can be
entered using the Watercut text box as a volume % of the total fluid. However,
you should be aware of the consequences of using watercut if you have already
defined an aqueous phase elsewhere, perhaps by entering an inhibitor solution,
such as aqueous methanol. In this case entering a positive volume percent of
water will alter the amount of water in the overall stream but leave the
composition of methanol unaffected, effectively changing the inhibitor
concentration. Entering 0% will leave water in the component list but at zero
concentration. Leaving watercut blank will leave any aqueous phase already
defined unaffected and is the most appropriate choice in the circumstances.
Adding water will not affect the hydrocarbon fluid characterisation although it
may, of course, affect the subsequent phase equilibria calculations.
Total amount of fluid

Your total fluid may comprise any combination of separator gas, separator liquid
and water. These will be combined based on the individual gas and liquid
compositions, the GOR and the water cut. The total amount of fluid text box
allows you enter the further specification of the overall amount of fluid, which is
then used to scale the compositions accordingly.
SARA Analysis
PVT Laboratories can often supply additional information on the fluid
composition in terms of a SARA analysis. This defines the relative amounts of
components which are saturates, aromatics, resins and asphaltenes. The amounts
of saturates and aromatics are used in some characterisation schemes. Our
current characterisation does not use this information but future extensions may
do so.
The SARA analysis is used by our asphaltene model. Currently, if you enter
amounts for resin or asphaltene these components will be added to your mixture
and will therefore affect your phase equilibria calculations. However, without an
asphaltene model you should not infer that you can calculate asphaltene
deposition.
In general the SARA Analysis should only be used with the asphaltene model. If
the amount of asphaltene or the resin/asphaltene ratio is unknown, it can be
estimated by the characterisation procedure by ticking the Estimate RA text box.
However, we recommend that you should use the experimental data if you know
them.
Characterisation
The characterisation procedure can be used to split or regroup the heavy end
from C6 to the heaviest SCN and to allocate physical properties to the resulting
pseudocomponents. From Multiflash 3.2 there are two characterisation
procedures, Infonanal1 (the original method) and Infoanal2 (the revised method
which also allows a n-paraffin distribution). If your problem has been stored in
an .mfl file then the choice of characterisation procedure will also have been
stored. Otherwise the first choice in the characterisation procedure is to choose
the characterisation method, by default this will be set to Infoanal2.
Perhaps the simplest case is to use the characterisation to allocate physical
properties to the SCNs already defined by the PVT Analysis. To do this, in the
Pseudocomponents section
Scroll Start pseudocomponents at until you reach the heaviest SCN in your
mixture

Scroll Number of pseudocomponents required to 1
Click on Do Characterisation
You should see a message to indicate that the characterisation has been
successfully completed
If you are using Infoanal1 then the pseudocomponents and their compositions
will be reflected in the main window . In this case the amounts should match
those entered. Thois will also be true for Infoanal2 but in this case we have
introduced an intermediate step which plots a comparison of the experimenta
analysis and the fitted distribution.
The physical properties related to any pseudocomponent may be viewed as usual

using the Tools/Pure Component Data option.
Splitting and regrouping the heavy end is very flexible. For example, to split the
heaviest SCN into five further fractions simply
Scroll Start pseudocomponents at until you reach the heaviest SCN in your
mixture
Or to reduce the total number of SCNs from 10 (C6 to C15 for example) to 5
Scroll Start pseudocomponents at until you reach a suitable starting point e.g.
C6
You can start the pseudocomponent split anywhere from C6 to the heaviest SCN
in your mixture. If you try to go beyond the heaviest SCN, you will be warned
that you are exceeding this value

Similarly, you can split the heavy end into any positive number of
pseudocomponents within the overall Multiflash limit of a maximum of 100
components in a mixture. If you try to go beyond this you will see errors
reported, such as
The names allocated to the pseudocomponent fractions will be generated by

Multiflash and be of the form C11-15. If you choose to use the revised
Infoanal2 characterisation without defining or estimating a n-paraffin
distribution the output will be similar.
If you wish to have a separate n-paraffin distribution you either enter the
experimental compositions using the appropriate form or supply a wax content
by either entering a known value or asking Multiflash to estimate this. You can
then characterise the n-paraffin distribution in the same way as you do for the
remaining fluid. In this case n-paraffin fractions are designated by the letter N,
e.g. N11-15, and fractions in the remainder of the fluid by the letter I. If the n-
paraffin distribution is estimated a warning message to this effect will be
displayed
The n-paraffin distribution need not be identical to the remaining fluid

distribution. For use with the Coutinho wax model our suggested default is C6
and 5 fractions for the main fluid and C6 and 15 fractions for the n-paraffin
distribution.
If an experimental n-parrafin distribution is supplied then the experimental and
fitted data for this distribution will also be provided.

Saving a PVT Analysis
Before you can save your fluid composition you must have carried out a
successful characterisation. Once this has been done your input file can be saved
as usual and when reloaded the original fluid composition will be displayed
allowing you try different characterisations.
Troubleshooting PVT Analysis

The PVT Analysis has been substantially improved since its first release. While
we have made every effort to test it there may be improvements we need to make
or problems we need to solve, so please get back to us if you spot any. Some
difficulties we have encountered are:
Sensitivity to characterisation
The distribution assumed in the original method is based on the Whitson Gamma
distribution function. Not all the PVT analyses we have tested are well
reproduced by this distribution and the revised method should provide a better
alternative. If you do see a warning that the default distribution parameter has
been used, then you should try the other distribution method or use the phase
envelope tracer to see how splitting and re-grouping pseudocomponents may
affect your phase calculations.
Presence of water
Defining a water cut using the PVT analysis form will alter the amount of water
in the overall stream but without changing the amounts of any components
which are not hydrocarbons and are not in the list of discrete components. It can
therefore affect the composition of an aqueous phase defined elsewhere in the
program.
Calculating petroleum fraction properties

If you know the input properties of the petroleum fraction or petroleum fractions
you wish to include in your mixture or your stream contains relatively few

pseudocomponents then you may choose to define the petroleum fraction
properties directly using the Select Components option.
First choose as your data source the Infochem Petroleum fractions correlations
from the Select Component dialog box. This will activate another dialogue box.
If you have a pseudocomponent reported to be C7 but have no physical

properties for this cut you can simply type in the carbon number and then click
on Add. The Pseudocomponent type should be left as Normal. The physical
properties required to characterise the fraction will be allocated from the
generalised table of petroleum fraction properties recommended by Riazi and Al-
Sahhaf.
Reference: Riazi, M.R. and Al-Sahhaf, T.A., Fluid Phase Equilibria 117 217
1996.
Multiflash will also allocate a name to the petroleum fraction, or you can enter a
name of your choice. You can look at the properties allocated to the fraction
either by using the Edit function
or through Tools/Pure Component Data in the main menu.

If you wish to specify the physical properties of the fraction yourself you may do
so. Activate the Petroleum fraction properties dialogue box and

fill in the name by which you wish to identify the fraction and any known
properties in the chosen units.
Select type of Pseudocomponent. The Normal option is the default for
petroleum fractions which are not asphaltenes or resins, but the latter two
categories are included for use in asphaltene modelling.
Then click on the Add (or Insert or Replace) button to add the fraction to the
selected list. Provided each fraction is identified by a different name then as
many petroleum fractions as you wish may be added to the selection, provided
the total number of components does not exceed 100, the current Multiflash
limit.
As discussed earlier the properties of any petroleum fraction are calculated from
the input data supplied. To do this we use a number of standard industry
correlations.
In Multiflash version 2.8 we changed the correlation for calculating the boiling
point temperature. If you have problem files saved from previous versions
(before 2.8) when you load these files the boiling temperature will be calculated
using the new correlation (unless of course the boiling temperature is one of the
input values). If for any reason you wish to calculate the boiling point from our
original correlation you can do so by entering the following command using
Tools/Command
Chardata infochar tbapi;
To ensure this is carried out correctly you first enter this command and then go
to Select Components to edit the petroleum fraction record. This should be
modified so that it only contains the original input specification, e.g. if you
originally supplied only molecular weight and specific gravity you should
remove the entries for boiling temperature, critical temperature and pressure and
acentric factor. Using Replace will then initiate recalculation. You can check
the results using Tools/Pure Component Data.
Note that there is a Units button available in the Select Components window to
change the units for entering data to define the fraction.
Editing petroleum fraction data

Having defined your petroleum fraction and carried out some calculations it is
possible you may wish to change the definition slightly. For instance you may
wish see how a different data input set alters a phase envelope. This should be
done using the Edit option in the Select Components dialogue box.
To edit and replace the petroleum fraction definition:
Return to the Select Components Window by clicking on the Select
Components button or using the menu option

Highlight the petroleum fraction you wish to edit by clicking on it in the
selected components section
Click on the Edit button, which will activate the petroleum fraction properties
dialogue box. This will show the current definition for the chosen fraction,
showing all possible input data, including properties derived from a more limited
input set.
Delete the values for any data you wish to recalculate, e.g. any of
the critical properties, then change or add values for the remaining
input definition.
Click on Replace
The new fraction definition will be loaded.
Alternatively, you may wish only to change a single property of a petroleum
fraction without recalculating any other properties which depend on it, perhaps
to determine the sensitivity of a calculation to that property alone. In this
instance, if you change the molecular weight the critical properties will not be re-
calculated.
Matching using petroleum fraction properties

Sometimes the properties calculated for your fluid will not correspond to known
or measured values for that property. Where the mixture includes petroleum
fractions it is possible to adjust some property of the fraction to modify a
property of the overall mixture. Typical mixture properties which can be
adjusted by altering fraction properties are the dew and bubble points, the
viscosity and, when the model is available, the wax appearance temperature.
The asphaltene deposition point is matched by adjusting the model parameters
rather than the properties of any fraction and will be discussed in the relevant
section.
Matching dew and bubble points

Your petroleum fraction can be re-defined by adjusting the properties of a
petroleum fraction to reproduce known experimental data, e.g. the dew point or
bubble point of a mixture.
This can be done automatically using the Tools/Matching menu option. The
matching function works with any number of fractions. In earlier versions of
Multiflash the user was limited to matching single dew or bubble points or a
single viscosity value. In Multiflash 3.2 this was expanded to allow the option
of entering a table of multiple values currently up to 10.
Typically you may know an experimental upper retrograde dew point. You
define your stream including one or more petroleum fractions and, if you wish,
check the calculated dew point pressure or temperature using a fixedphase
fraction flash, see Fixed phase fraction flashes on page 118.
Our example has 9 petroleum fractions, the properties of the heaviest, C20+, are
shown below.

If the calculated dew point does not match the experimental values, activate the
matching facility using Tools/Matching/Dew point menu option.
and enter the values for one or more experimental dew points and the type of
dew point you are calculating (the Upper retrograde solution is the default
setting for dew point). Click on the Match button and the acentric factor of the
fractions will be adjusted until the calculated and experimental values match.
A plot will show a comparison of the experimental data fitted data

and the adjusted acentric factors will be reported in the main window together
with the critical temperature and pressure.
match table dewpoint upper retrograde temperatures 305.35 340.95
398.55
442.55;pressures 462.800000 401.600000 303.500000 229.600000;;;
PETROLEUM FRACTIONS PHYSICAL PROPERTIES:
TC/K PC/bar ACENTRIC FACTOR

ACENTRIC FACTOR 2
11P 515.61 31.293 .23415 -.11001
12P 545.10 31.030 .25541 -9.89404E-02
13P 570.76 29.346 .28038 -8.13332E-02
14P 597.63 27.167 .31119 -5.73618E-02
15P 617.81 25.482 .33671 -3.64683E-02
16P 643.74 23.564 .36988 -8.14670E-03
17P 687.08 20.486 .43067 4.59179E-02
18P 747.39 16.427 .52923 .13653
19P 811.89 13.044 .63988 .24205
EXPERIMENTAL AND CALCULATED VALUES: DEWPOINT
T(exp)/K P(exp)/bar P(calc)/bar
305.35 462.800000 455.265209
340.95 401.600000 407.966543
398.55 303.500000 315.039181
where C20+ is the 19th component. The adjusted acentric factor will be relected
in the pure component record

The new fraction properties can be saved using File/Save Problem Setup.
ACENTRIC FACTOR 2 values may not be displayed if they do not produce a
better fit to the saturation line.
Bubble points can be matched in a similar manner and similar plots generated,
either for the whole phase envelope or over a selected temperature or pressure
range.
Matching wax appearance temperature

The method used for matching the wax appearance temperature (WAT) to
experimental data is to adjust the melting temperature of the petroleum fractions
in the mixture. From Tools/Matching menu, Select Other Phases to activate the
Other Phases dialog box. In principle this option can be used to match any fluid
phase including wax.

Select the wax phase from Select Phase drop-down list and fill in the values for
the experimental WAT at a given pressure in the correct units. Then click on the
Match button and the melting temperature and the enthalpy of melting of
petroleum fractions will be adjusted to match the WAT provided. The adjusted
melting temperature or enthalpies will be displayed in the main windows:
fixedphase WAX unspecified 0. Molefraction;
match phasefraction;
TM/K DHM/J/mol
7P 176.49 5630.8
8P 183.30 6038.2
No plot is generated when Other Phases are matched.
The new fraction properties can be saved using File/Save Problem Setup for
future use. With the new Coutinho wax model a similar adjustment is made but
in this case only to the n-paraffin pseudocomponents as it is these which form
the wax phase.
Matching liquid viscosity

This facility allows you to match a known liquid viscosity. It cannot be used to
match the viscosities of gas, water or solids.
From the Tools/Matching menu Select Liquid Viscosity

Choose the correct phase from the list of possible phases and enter the
temperature and pressure conditions and the liquid viscosity or viscosities to be
matched. The matching procedure works by altering the reference viscosity of
the fractions and these will be reported in the main window, together with a
comparison of the experimental and fitted values of viscosity. For example
REFERENCE VISCOSITY/cP
11P .24412
EXPERIMENTAL AND CALCULATED VALUES: VISCOSITY
T(exp)/degC P(exp)/bar Visc(exp)/cP Visc(cal)/cP
114.40 332.000000 .456000000 .446388733
114.50 290.300000 .430000000 .425686970
114.40 241.700000 .412000000 .401764279
114.40 219.300000 .393000000 .390433458
114.50 189.800000 .380000000 .375073303
114.40 187.800000 .382000000 .374320636
114.40 173.100000 .388000000 .397174169
114.90 157.400000 .408000000 .422478903
114.40 125.100000 .469000000 .486002624
114.90 65.7000000 .652000000 .647117892
Prior to this a comparison plot will be generated for any any isotherm or isobar
for which experimental data was supplied. If only a single viscosity point is
matched the plot will be supplied for the isotherm.

The reference viscosities will also be reflected in the pure component data record
for the petroleum fractions.
The matching facility will attempt to match the data supplied whether or not it is
appears physically realistic. No warning will be issued if liquid viscosities
increase with increasing temperature.
Problems defining a petroleum fraction

The properties you enter to characterise a petroleum fraction will be checked
when you click on the ADD button to select it. If they are physically unrealistic
or cannot be processed by the petroleum fraction suite of correlations you will be
warned and the fraction will not be accepted for selection. The obvious
problems will be entering a negative number for a quantity which must be
positive, e.g. molecular weight, specific gravity or acentric factor. The warning
message will be self-explanatory
It is possible for a temperature to be negative in the chosen units, but if it is also

negative in absolute units a slightly different message will appear
The best advice we can offer is to make sure that you check that the units
(displayed next to each of the input text boxes) match the numerical values you
are putting in. A different section will discuss how to change units, see
Changing units on page 135.

Problems when matching
It is possible that matching to a particular property, such as the bubble point,
may require a significant change to the properties of the petroleum fractions. If
the petroleum fraction property that is adjusted is altered by more than 10% then
you will see a warning message. For example:
match bubblepoint;
*** WARNING -13581 ***
Adjustment to petroleum fraction properties is
probably physically unrealistic
However, the adjusted property, e.g. acentric factor, may still be reasonable, in
which case you should continue with your calculation. If you consider the
adjusted properties to be physically unrealistic you need to check the
compatibility of the characterisation and bubble point data you have entered.
If Multiflash is unable to reconcile the petroleum fraction characterisation with
the value to match the error message will be
match bubblepoint;
*** ERROR 20565 ***
Quadratic extrapolation failed to improve solution
*** ERROR 20404 ***
The Matching procedure has failed
*** ERROR 448 ***
The matching calculation has not converged

Input conditions
Introduction
Once you have chosen the model for your mixture and selected the constituent
components, the next step is to specify the input conditions for the problem. In
Multiflash these are
Component compositions
Temperature
Pressure
Volume
Enthalpy
Entropy
Internal energy
The component compositions must be specified but only a subset of the other
conditions are needed depending on the calculation to be carried out. All input
conditions must be specified in the correct units. The units currently selected will
be defined adjacent to the relevant text box or drop down table. For information
on how to change the units see Changing units on page 135.
As you may wish to change the input conditions frequently, the majority are
grouped together in the Conditions section of the main window.
Input conditions can be entered in the Conditions section or can be supplied in

the problem setup file.
Specifying compositions
Component compositions can be specified or modified in three places.
Normally, they will be defined in the drop down table under Compositions.
However, it is possible to enter them under the PVT Lab. Fluid Analysis Form
(see PVT Analysis on page 110) or to enter the composition of an inhibitor
through the Inhibitor Calculator (see Inhibitor calculator on page 79).
User Guide for Multiflash for Windows Input conditions 111

Note that in the Composition To specify the amount of any component in a mixture using the drop down table
drop down table component under Compositions activate the table by clicking on the Compositions button.
names which contain a space The table will list each of the selected components and the compositions should
have the space replaced by an be entered in the right-hand column, in the units designated. If the composition
underscore. has been defined in the problem setup file it will appear in the table.
The compositions can be changed by overwriting any of the set values.
In the drop down table all input units for compositions (amounts) are absolute
units. If you wish to enter mole fractions then do this with the units set to mole,
but you must check yourself that they add up to one. Otherwise they will be
totalled in moles and the fractions scaled accordingly.
When using the stream type option to allocate a selection of the components in
the overall stream to a sub-stream the amounts of the components in that sub-
stream remain those designated in the Composition drop down table. If they are
altered there this will be also be reflected in the overall composition of the
stream.
N.B. In the Inhibitor Calculator and the PVT Analysis Forms the compositions
are specified as mole, mass and occasionally volume %. When specifying
composition using the PVT Analysis Form you do have the opportunity to
normalise the compositions if they do not add up to 100.
Certain criteria apply to all three ways of specifying composition, although the
warning messages may differ slightly. The messages shown here are generated
from the Composition drop down table.
You must define a positive amount for at least one component in a mixture for
any flash calculation to be successful, although you may set amounts for some
components in a mixture to zero in order to remove them temporarily from the
mixture definition.
If no composition is defined, i.e. all entries are set to 0, then you will see errors
reported when activating the flash calculation, starting with
*** ERROR 20135 ***
The total number of moles in the feed is zero
If you enter an unacceptable value, e.g., a negative amount in the composition
column you will be asked to re-enter the amount once you try to activate a flash
calculation or enter another input condition, for example
Specifying temperature, pressure and volume

For most of the standard flashes you must define either temperature or pressure
plus one other input variable. For an isothermal flash, of course, you need both
P and T.
The numerical values for temperature, pressure and volume should be entered in
the appropriate text box, in the correct units. If they have been set in the
problem setup file they will be displayed in the text box.
The values entered are checked when you move to another input condition or
attempt to do a calculation or display another dialogue box. If the input pressure
112 Input conditions User Guide for Multiflash for Windows

or volume entered is unacceptable (perhaps a negative value) or the absolute
temperature equivalent to any entry is unacceptable then you will be asked to re-
enter the input condition as with the composition.
If you fail to enter temperature, pressure or volume and this is required for the
flash calculation chosen then the appropriate error message will be shown in the
results window. For example, if you try to activate an isothermal flash at fixed
P,T specifying a pressure but not specifying an input temperature the following
error will be reported
Flash at fixed P and T:
*** ERROR 259 ***
Temperature not specified - Calculation not carried
out
Specifying enthalpy, entropy and internal energy

These input conditions are used when calculating isenthalpic and isentropic
flashes and flashes at fixed internal energy. The datum points for enthalpy and
entropy set the value of both to zero for the perfect gas at 298.15K and 1 bar.
Consequently enthalpy, entropy and internal energy can take both positive and
negative values. There is therefore no check on the value entered for any of
these three input conditions. If the value entered for any one of them is
physically unrealistic you may fail to get a converged solution for a flash
calculation and the error message will report this failure.
As with temperature, pressure and volume if you fail to set an input value for
any of these variables and choose a flash calculation involving them you will see
the related error message warning that they have not been specified and that the
calculation has not been carried out.
Troubleshooting - input conditions

It is always possible to make mistakes when entering numerical values. You
should therefore check carefully, particularly if you feel the results appear
unusual, that
the values for the input conditions are correct
they are in the correct units and that
if they remain fixed for the flash calculation chosen, they appear
correctly in the output
Another problem relating to units may occur if the input conditions are set in a
problem setup file, but the input units are not specifically defined. In this case,
when the file is loaded, it will be assumed that the values correspond to the units
currently set in Multiflash. If this is not your intention it will clearly lead to an
incorrect result in your terms, but not necessarily to an error in Multiflash.
TIP If you wish to include the input conditions in a problem setup file you should
also define the input units for the conditions specified. The units specification,
as well as the numerical value, will be displayed in the conditions window.
User Guide for Multiflash for Windows Input conditions 113

Calculations (flashes)
Introduction
All the calculations carried out in Multiflash are flash calculations. This is true
even when you are only interested in obtaining the saturated liquid properties of
a pure component: the initial calculation in this case is finding the bubble or dew
point at a fixed temperature.
Multiflash is designed to carry out a series of single flash calculations except for
the phase envelope generator where a series of flashes are performed . Before
activating a calculation you must specify the components, compositions, model
and input conditions appropriate to the flash. After you have performed a
calculation you then make any changes you want to any input variable and
activate the flash again. When the phase envelope function is used to plot any
phase line the results of the individual flashes carried out are shown in the main
window. There is currently no other facility to generate automatically table style
output. Alternatively if you wish to generate tabular output frequently this can
be done easily using our Excel spreadsheet interface.
Of course, if you wish to calculate a series of flashes at changing conditions you
can set them up in a problem setup file. Once this is loaded all the flashes will
be calculated without further interaction on your part and you can scroll through
the output in the results window.
The basis of a flash calculation.

In a flash calculation any two of the following variables
Temperature (T)
Pressure (P)
Volume (V)
Enthalpy (H)
Entropy (S)
Internal energy (U)
Amount of a phase
are fixed . Based on the thermodynamic principles that at equilibrium
The fugacities of each component in all phases are equal
The temperatures of all phases are equal
The pressures of all phases are equal
User Guide for Multiflash for Windows Calculations (flashes) 115

and the solution satisfies the set constraint (the two fixed variables remain the
same) then the flash calculation allows you to determine, subject to the
constraints imposed, the number and type of phases present and the composition
and properties of those phases.
Multiflash offers a comprehensive range of flash calculations, a list of which is
given below. The most widely used of these are then discussed individually.
Flashes available in Multiflash

The following flashes may be calculated in Multiflash.
Standard flashes
P,T flash Isothermal flash
P,H flash Isenthalpic flash at fixed pressure
T,H flash Isenthalpic flash at fixed temperature
P,S flash Isentropic flash at fixed pressure
T,S flash Isentropic flash at fixed temperature
H,S flash Flash at fixed enthalpy and entropy
P,V flash Isochoric flash at fixed pressure
S,V flash Isochoric flash at fixed entropy
T,V flash Isochoric flash at fixed temperature
U,V flash Flash at fixed internal energy and volume
P,U flash Flash at fixed internal energy and pressure
T,U flash Flash at fixed internal energy and temperature
Bubble and dew point flashes
P, Dew point Dew point at fixed pressure
T, Dew point Dew point at fixed temperature
P, Bubble point Bubble point at fixed pressure
T, Bubble point Bubble point at fixed temperature
Fixed phase fraction flash
P, Fixed phase fraction Flash with a fixed amount of a
specified phase and fixed pressure
T, Fixed phase fraction Flash with a fixed amount of a specified
phase and fixed temperature
Tolerance calculation Calculates the amount of a second stream
which needs to be added to a stream in order
to meet a fixed constraint e.g. amount of
inhibitor to suppress hydrate formation
Phase envelope A series of flashes to generate a phase
diagram for any phase present
The fixed phase fraction can be specified in mole, mass or volume
units. However, the particular example of tolerance calculations is
still restricted to molar units.
Chemical Equilibrium
Equivalent flashes to those described above but also taking into account
simultaneous chemical equilibrium
P,T Chemical Equilibrium
116 Calculations (flashes) User Guide for Multiflash for Windows

P, Dew Point Chemical Equilibrium
T, Dew Point Chemical Equilibrium
P, Bubble Point Chemical Equilibrium
T, Bubble Point Chemical Equilibrium
All the above flashes may be activated by clicking on Calculate in the menu
bar, then clicking on the flash type, then clicking on the particular flash. A
dialogue box for entering additional information is activated for the fixed phase
fraction flashes.
The most widely used flashes can also be activated by clicking on the
appropriate button in the tool bar.
Isothermal (P,T) flash

A calculation of the equilibrium conditions of a given mixture at specified
pressure and temperature is called an isothermal or P,T flash. It allows you to
determine the number and type of phases present and the properties of those
phases. It is the most widely applicable and the most reliable of the flash
calculations. It also has a unique solution.
To activate an isothermal flash for a given mixture
Ensure you have chosen a model
Enter the temperature and pressure in Conditions
Select Calculate in the menu bar
Select Standard Flashes in the sub menu
Select P,T flash.
Alternatively click on the tool bar button, in place of the last three steps.
Isenthalpic flashes
These are flashes at fixed enthalpy. The most useful is the P,H flash which is
used when studying flow through valves or pipelines. A typical calculation is to
Determine the enthalpy of a stream at a given P,T (isothermal flash)
Enter the calculated enthalpy in the Conditions section
Drop the pressure by entering a lower pressure under Conditions
Click on the button or specify P,H flash from the menu bar.
The P,H flash also has a unique solution.
You can plot the phase boundaries for given constant enthalpy values.
Isentropic flashes
The isentropic, fixed entropy, flashes are used when you are looking at adiabatic
and reversible processes such as a turbo expander where you would use the P,S
flash. The H,S flash has applications in the turbine industry.
As with the isenthalpic flash, enter the value for the entropy which you want to
remain fixed in the Entropy text box, and enter the value for the other variable
(usually P or H). The P,S flash may be activated through either the tool bar
button or the menu, but the latter is the only option for activating the H,S flash.
You can plot the phase boundaries for given constant entropy values.

Isochoric flashes
The isochoric or fixed volume flashes are used when looking at closed systems,
such as vessels. The two most used are the T,V flash where you know the
temperature and the U,V flash where you know the internal energy. Neither of
these flashes have tool bar buttons assigned to them, both are activated only
through Calculate in the Menu bar.
You can plot the phase boundaries for given constant volume values.
Bubble and dew point flashes

In a simple two phase system a dew point is the first point at which liquid
appears. This will be a temperature if the pressure is fixed and a pressure if the
temperature is fixed. Similarly a bubble point denotes the first point at which
gas appears. In a multiphase situation it is possible to have more than one dew
point (you will probably have more than one liquid phase). The choice of the
dew point flash will result in Multiflash calculating the first, or primary, dew
point found at the given temperature or pressure. As dew and bubble points are
particular applications of a fixedphase fraction flash, secondary dew points can
be calculated by specifying the name of the phase, setting the fixed amount of
the phase to zero for liquids, 1.0 for gas, and carrying out the fixedphase flash at
a given pressure or temperature. Simple dew and bubble points can also be
calculated this way and fixedphase flashes are discussed in more detail below.
Dew and bubble point flashes for two phase systems (or the bubble point and
primary dew point flash for a multiphase system) can be activated either from
Calculate in the menu bar or tool bar buttons,
and for bubble point flashes
and for dew point flashes.

Depending on the temperature or pressure specified and where this is in relation
to the phase envelope it is possible that the problem posed will not have a
solution.
Fixed phase fraction flashes

This is the general application of a flash where the temperature or pressure is
fixed plus the fraction of one of the possible phases for a given mixture. The
phase fraction may be defined in molar, mass or volume units. The fraction may
take any value between 0 and 1, it does not have to be 0.0.
Phases
Multiflash is a multiphase phase equilibrium program that can handle up to nine
phases at any time with the current configuration. Any individual calculation
will consider the possibility of all specified phases but the maximum which may
exist together at equilibrium is limited to seven. The phase types that are
included in the current version of Multiflash are
Vapour
Liquid
Condensed (pure solid)
Hydrate
Wax
asphaltene

It is clearly possible to have more than one of all these types except vapour.
However, the software and models are structured such that it would not be
sensible to define more than one wax or asphaltene. In order to identify each
phase uniquely they are assigned names and, in some cases, key components, see
What the model definition means on page 46. In the Select Models option and
in the standard model configuration files (.mfc) supplied we use a standard set of
names for the different phases.
Phase names
The standard phase names are:
GAS vapour phase
LIQUID1 first liquid phase
LIQUID2 second liquid phase
WATER liquid phase with key component water
ICE solid phase with freeze-out model used for water
HYDRATE1 hydrate phase, structure I
HYDRATE2 hydrate phase, structure II
HYDRATEH hydrate phase, structure H
WAX wax phase
ASPHALTENE Asphaltene phase with key component asphaltene
If you apply the freeze-out model to any phase the default name is generated by
adding solid before the component name, e.g. SOLIDDECANE.
Using the command language you can of course allocate your own names to any
of the phases.
If you have created your own problem setup file you may have called these
phases by different names. In which case these names will appear in the
program in place of our standard nomenclature.
The phase names are used to identify the different phases when carrying out
fixed phase flashes and to identify the phases in the Multiflash output.
Key components
A key component helps to identify a particular phase. The rule used is that the
key component should be present in the phase to the maximum amount relative
to the total mixture composition. If the component name is preceded by the
keyword not , this means that the component should be present in the minimum
relative concentration.
The model sets and model configuration files supplied identify one liquid phase
as having water as the key component and the other two liquid phases in terms of
not being the water phase.
A key component is only needed when a flash calculation must identify a phase
uniquely (e.g. search for a particular phase fraction). Examples are the
fixedphase fraction flash or a phase envelope calculation.
If you request any of these calculations for a phase, the key component of which
is missing, an error message will be returned. For example if you try to calculate
a water dew point when there is no water in your stream the you will see the
following message:

The other two liquid phase descriptors are not distinguished in terms of key
component as these are set in the model definitions prior to any components
being defined. In most cases the fixedphase fraction flashes and phase envelope
calculations will solve without any additional information. However, if the lack
of unique identification may lead to problems in reaching the correct solution a
warning will be issued.
*** WARNING -20131 ***
Key component not specified for multiple
liquid/solid phases
To prevent potential problems you should nominate a key component for at least
one of your two non-aqueous liquids. This can either be in terms of one of your
specified components e.g.
key liquid1 heptane;
or we have allowed for two more general options, heaviest and lightest, e.g.:
key liquid1 heaviest;
key liquid2 lightest;
Whilst the latter may appear convenient you should remember the rule that the
key component should be present in the phase to the maximum amount relative
to the total mixture composition. If you have a mixture rich in methane then
when the first liquid forms it may have more methane than the heaviest
component and thus be labelled liquid2. For the same reason when specifying a
liquid in terms of a specific component it is often more useful to choose one in
the middle on the component range, e.g. heptane, rather than the heaviest
hydrocarbon.
Another occasion when you need to be particularly careful in your choice of key
components is when using an Excel spreadsheet to carry out linked flashes or
recycles where the composition of your streams can change significantly.
Defining the fixedphase flash

To activate the fixedphase flash option you either click on the fixedphase flash
button for fixed pressure or fixed temperature or activate the option

through Calculate in the menu bar.
Either will activate the following dialogue box. The number of possible phases
for your specified problem will be shown. This example, which is for a hydrate
I/II calculation, has seven phases. The equation of state model sets usually
define four phases, (GAS, LIQUID1, LIQUID2 and WATER) whereas the
activity coefficient models are usually defined with LIQUID1 and LIQUID2 or
GAS and LIQUID1 with the option to add extra liquid phases.

To see the list of possible phases click on the arrow to the right of the Select
Phase list box. Select the phase you want to fix by clicking on the phase
name; this will then appear as the selected phase.
Then select the basis for the fixed phase fraction flash. The options are mole
fraction, mass fraction and volume fraction for general use and nucleation for
use in hydrate calculations.
Then enter the phase fraction you want to fix in the text box below. This
fraction must be between 0 and 1. Usually it will be zero, i.e. you are looking
for the pressure or temperature (depending whether you fixed T or P) at which
this phase first appears. However you can also use this facility to look for the
conditions at which there is a specified fixed amount (>0) of any phase. Finally
click on Do flash.
For systems exhibiting normal dew and bubble points the section to the left of
the dialogue box labelled type of solution can remain as it appears, with the
Normal (default solution) option button selected. However, some systems, such
as gas condensates can exhibit more complex phase diagrams, as shown below.
For normal systems if you reduce the pressure along an isotherm from the
liquid or dense gas region you reach its bubble point, where the gaseous
components no longer remain dissolved in the heavier liquid components and
separate off as a gas.

In gas condensates the gaseous components are in excess and the heavier liquid
components in the minority. In this case, as the pressure drops, the liquids drop
out of the gas phase and eventually, as the pressure is reduced even more, the
liquid components evaporate again. This is known as retrograde. condensation.
For a normal fluid there is only one solution (calculated pressure) for the dew
point at any given temperature. However, for systems exhibiting retrograde
condensation there may be more than one solution. Consider the phase envelope
above, which has a large retrograde region. Taking a temperature of 300oF, for
example, there are two dew points; one at 2.5 psia (normal dew point) and one at
2977 psia (upper retrograde dew point). Multiflash, with the default setting of
normal, will always search for the former when the gas phase fraction is set to
1.0 (to simulate the dew point). To search for the second solution the Type of
Solution option button must be set to upper retrograde.
With the addition of new models other Types of Solution become important.
Experience with the asphaltene model has shown that unspecified should be set
when solving for asphaltene flocculation.
Otherwise, it is very difficult to specify exactly when different options for the
type of solution setting will be appropriate. This depends on whether the
pressure or temperature is being fixed and where the critical point for the
mixture is on the phase envelope in relation to the cricondentherm (the maximum
temperature at which a two phase mixture can exist) and the cricondenbar (the
maximum pressure at which a two phase mixture can exist). The phase envelope
above is labelled with the solution types used to calculate the phase envelope at
fixed temperature. The maximum pressure at which the liquid (condensate)
drops out of the gas is the retrograde dew point. The lowest pressure at which
the condensate has all evaporated again is termed the normal dew point.
TIP If you find a situation where you get failures for dew and bubble point
calculations, or the solutions are not in the region you expect, then it is worth
carrying out some isothermal (P,T) flashes or to plot the phase diagram.
Tolerance calculations
Tolerance calculations are used to determine the amount of a component or
mixture that must be added to the original stream to achieve a given phase split.
A typical application is to determine how much inhibitor is required to suppress
hydrate formation. Another example might be to determine the amount of water
needed to saturate a gas. Tolerance calculations are carried out at fixed
temperature and pressure and for a fixedphase fraction specified in moles.
To carry out a tolerance calculation specify the model and the components in
your stream. These should include the component or components for which you
wish to determine the amount to be added. In the Composition table specify the
composition for your mixture. The component/components for which the
tolerance calculation is being carried out need not be there in zero amount if they
are already present in the stream. However, it is more usual to set their
composition to zero, for example zero amount of methanol when you wish to
calculate the amount needed to inhibit hydrate formation. Using
Calculate/Tolerance Calculation open the subsidiary window

In the Tolerance Calculation window set the phase and the fraction of that phase
for the fixedphase element of the flash. Then select the Composition of Second
Fluid tab. In the table enter the amount of the single component (usually 1.0) or
the composition of the mixture to added to the main stream to meet the
constraint set.
Assuming you have already set the temperature and pressure click on the
Calculate button. The results in the main window will show the amount of
second fluid to be added to the original stream to meet the set constraints. In the
example this is the amount of methanol to be added to the original inhibitor free
stream to meet the condition of zero hydrate phase.
Tolerance Calculation:

Provide a starting estimate
If you feel you have specified the flash, correct input conditions and correct type
of solution but convergence errors are still being reported it may be worth
providing a starting guess for temperature or pressure. This is done by selecting
Use Starting Values from Select in the menu bar. The command line
set startvalues
will be shown in the results window.
Activate the flash option.
The temperature or pressure, whichever is appropriate for the flash option
chosen, given in the input conditions text box will be used as the starting value
for the calculation.
To turn off the starting value, repeat the step above and the command line will be
reported on the results window to show you that Use Starting Values option has
been switched off.
set nostartvalues
Unfortunately in the vicinity of the critical point the use of starting values may
not be sufficient to give convergence as calculations in this region can be
particularly sensitive to composition.
Phase diagrams
A major addition to Multiflash was the ability to calculate and plot phase
envelopes. It is possible to trace any phase boundary including gas, liquid and
solid on pressure-temperature co-ordinates. A V/L Autoplot function traces the
primary dew and bubble point curves. You should note that the phase envelope
should only be used for models based on an equation of state (or at low pressures
for activity models).
In version 2.9 we added the ability to trace selected phase boundaries on the
basis of mass or volume fraction in addition to mole fraction and the nucleation
boundary. In 3.0 we increased the flexibility of the phase boundary tracer to
include the plotting of constant enthalpy, entropy, volume or free energy
boundaries. In 3.1 we improved the boundary tracer to handle cases where the
line crosses a phase boundary at which there are no degrees of freedom
according to the phase rule. The common example is the vapour-liquid
saturation line for a single component. In version 3.2 we have generalised the
plotting facility so that for any chosen phase boundary it is possible to plot any
phase or property against another. The 3,3 release of the phase envelope has not
made any technical changes to phase boundary calculation but includes a useful
improvement which automatically changes the colour of any new boundary.
The Phase envelope is activated through the Calculate/Phase Envelope menu or
using the phase envelope button, .
The resulting window has three sections. The first

allows you to generate either the vapour/liquid phase envelope automatically or
to set a specific phase boundary e.g. WATER in zero amount to define the water
dew point line. You should also choose the appropriate Type of Solution as
discussed previously, e.g. unspecified if you want to trace the asphaltene
flocculation boundary above the bubble point pressure. If the VLE AutoPlot
fails to trace the full phase envelope the liquid and gas phase boundary lines can
be plotted individually.
You may then select a variety of properties of that phase to be plotted, including
phase fraction.
If you choose to plot any of these then you will be reminded of the current unit
setting for the property when you enter the value.

The second section provides the initial conditions for any phase boundary and
the conditions and direction for the boundary search. Experience has shown that
using increasing pressure is a useful default. If the user does not set an initial
value for the pressure a default value of 1 bar, or the equivalent in the units
chosen, will be set. This value is only shown in the text box once the boundary
has been plotted.
While one bar is usually an appropriate default to start the plot you should also
be aware that on some occasions there may not be a solution for a particular
boundary at this pressure and it may be necessary to vary initial conditions to
start the tracing of the phase boundary.
If the boundary still proves difficult to trace starting values for the temperature
or pressure as appropriate can be provided. For the phase envelope calculator the
starting value is provided by entering a guess in the text box, i.e. a value for
the temperature if you are defining pressure.
The final section allows you to set P,T boundaries for the calculation and to set
the properties you wish to see displayed on the x and y axis. For normal phase
envelopes these will be temperature and pressure.

In previous versions of Multiflash as well as the plotted boundary the
temperatures and pressures generated were displayed in the main results
window. This display also includes values for additional properties at these T,P
conditions.
These include volume, enthalpy, entropy, internal energy and phase fractions of
any other phases present as specified in the model specification for the problem.
Any of these properties plus temperature and pressure can be plotted against any
other. The choice is available from the drop down menu.
A typical example might be a VLE plot for a hydrocarbon fluid with gas present
in zero mole fraction. The axes will be pressure versus temperature.

It is also possible to look at the liquid mole fraction as a function of temperature
Before the new plot is displayed you will be reminded that you have altered at
least one of the axis properties and that boundaries plotted on the previous axes
will be lost.
If you wish to return to the standard P,T axes to plot you must remember to alter
the axes yourself in the Frame tab, they will not be reset automatically.
The Frame tab allows you to change the maximum number of points calculated
at any one time. The default is 100. If, when plotting any phase boundary it is
possible to calculate more points, then a displayed message will allow the phase
envelope calculator to continue or to stop at any point.

The phase envelope will be shown at the same time as this message so that you
can make an informed decision as to whether more points would be beneficial.
The phase diagram window also remains open even when you return to the main
window to carry out further calculations. When you want to close it click on the
Close button.
If the calculations have reached any limit within the 100 points the message will
not appear.
Any critical points are labelled with a C and discontinuities, where phase
boundaries cross, are marked with a D.
Similarly, the individual flash results which appear in the first three columns in
the window are marked with C or D so that the numeric values at these point can
be determined.
Phase envelope output:
T/K P/bar
71 380.475 97.055
72 378.655 99.477
73C 377.068 101.23
74 375.109 103.10
75 371.322 105.97
The first column is the number of the point plotted.

N.B. When plotting phase boundaries with a high level of salt component in the
stream, to obtain sensible results you should allow a solid salt phase to form. To
do this set up a freeze-out model for the salt component using the Select/Freeze-
out Component option, see The Freeze-out model on page 48.

Customising the phase envelope plot
From the Phase Envelope window you can choose to keep or delete the most
recently plotted phase boundary or to clear the whole plot. If you do not clear
the plot any new phase boundaries will be added to the existing plot. This is a
useful way to look at how multiple phases relate to each other or to plot quality
lines (lines for differing amounts of a liquid phase) for any phase envelope.
The plot is always cleared if you Clear the problem setup.

Individual plots can be customised. The Options button allows you to change
the colour, type and legend for any boundary. It also allows you to delete any
phase boundary. Tool bar buttons within this window also access the Graphics
Server with the facilities to edit the graph and axes titles, move the axis to left
or right, overlay with experimental data points etc.
Write to Excel
Although you can call all Multiflash functions directly from an Excel
spreadsheet, including the Phase envelope function, you can also transfer the plot
and phase boundary points to Excel. Once you are happy with a plot clicking on
Write to Excel will generate a spreadsheet with a Chart corresponding to the
tabular values reflected in the main window with the values themselves posted to
a worksheet.
The Write to Excel facility is supported for Excel 97, 2000 and XP but not for
Excel95.
Property output in Multiflash

Multiflash provides several levels of physical property output. The default is to
provide information on phases, compositions, thermal and volumetric properties.
There are five higher levels providing more output in which fugacity coefficients
and activity coefficients relative to each component in each phase are recent
options. In version 3.3 the ability to calculate and display diffusivity has been
added. The output can also be reduced to a minimum of phases and
compositions.

The level of output can be set using the Select/Property output option. The
following dialogue box will be displayed
Activity coefficients may not be a valid property for all components in all
phases. This will depend on the component and the model. If the property is not
valid N/A will be displayed.
The default setting is equivalent to the first two options being selected. To
reduce the output click on OK with all options deselected. Otherwise select the
properties for which you want output. If you choose Heat Capacity and Speed of
Sound the phase amounts and composition plus the volume and thermal property
output are also automatically selected. Note that the thermal properties relative
to elements option is not available without the first two options being selected.
Examples of the property output options are shown in Calculation output on
page 158.
If you are doing chemical equilibrium calculations you may wish to see the
values of thermal properties (enthalpy, entropy, internal energy and Gibbs
energy) relative to elements in their standard states.
Troubleshooting - flash calculations

This is the most difficult area for which to give general guidance. Multiflash is
capable of handling complex mixtures which may exhibit multiphase phase
equilibrium. The reported errors are likely to be of the type
Bub point at fixed P:
*** ERROR 20292 ***
Cannot find converged point - max. iterations
*** ERROR 20024 ***
Cannot find starting point for calculation - there
may be no solution.
*** ERROR 344 ***
The flash calculation has not converged
The difficulty is to assess the reason for the error and how best to investigate the
cause and take corrective action.
An error may be reported when there is genuinely no solution to the problem
posed. The error above, for example, resulted from asking for a bubble point at a
pressure above the cricondenbar for the gas condensate discussed earlier. As
you can see from the phase diagram presented there is no bubble point at this

pressure as it is above the pressure at which the two phase mixture will exist. In
general you will not be able to solve bubble or dew point problems at pressures
above the cricondenbar or temperatures above the cricondentherm.
Another type of phase envelope where problems can arise is shown below
As you can see the phase envelope turns up at low temperatures and high
pressures. This is also typical of phase envelopes with a significant amount of
hydrogen where you may not find a solution for the bubble point at low
temperatures.
What can you do if the method used to find a solution is not capable of solving
the problem posed? There are various strategies which may help:
Plot the phase envelope

This facility is an excellent way of determining the phase boundaries and what
phases you might expect to be present under given temperature and pressure
conditions. For information on plotting the phase envelope see Phase
envelope on page 141.
However, plots at high pressure based on activity models will not be meaningful.
Use the P,T flash

The P,T flash is the most reliable of the flashes and the least likely to fail. It can
be used where you are experiencing problems with other flashes to see where
you are in terms of the phase envelope.
Even the P,T flash may occasionally have problems. Again hydrogen containing
mixtures can pose difficulties; it may not be possible to find a solution where the
mixture is all liquid even using an isothermal flash.
Limit the number of phases

Multiflash is designed to consider the possibility of all the phases specified in the
model set (or model configuration file or problem setup file) being formed and to
establish the most stable solution. The model sets and *.mfc files for the
equations of state are generally configured for four phases, GAS, LIQUID1,
LIQUID2 and WATER. If you are having problems finding a solution and think
you know there are fewer phases, possibly only GAS and LIQUID1, or
LIQUID1 and LIQUID2, then it may be worth while reducing the number of

phases to be considered. This can be done by switching off one of the phases in
the Model Set dialog box.
Consider all types of solution

As we have discussed above, for complex mixtures and phase diagrams you may
not find the solution in the region you want by the normal solution route. Plot
the phase envelope or carry out some P,T flashes to see what type of phase
envelope you have and whether you should be seeking retrograde solutions. For
retrograde solutions the terms upper and lower have no absolute meaning, they
merely determine whether the search is for a lower or upper temperature or
pressure.
Provide a starting estimate

If you feel you have specified the correct input conditions but convergence errors
are still being reported it may be worth providing a starting guess for
temperature or pressure see Provide a starting estimate on page 141.
Provide a key component

As we have discussed earlier, Key components on page 136, default key
components are defined for the standard phase descriptors. If difficulties occur
in uniquely identifying a phase then providing a more specific key component
for a phase may help find the solution.
Chemical reaction
Multiflash has a chemical equilibrium module which allows the simultaneous
calculation of phase and chemical equilibrium. The phase equilibrium is
currently limited to equilibria involving combinations of one gas phase, one
liquid phase and any number of pure solid phases. The flash options available
are
P,T Chemical Equilibrium
Dew Point Chemical Equilibrium

Bubble Point Chemical Equilibrium
These are all activated from the menu route Calculate/Chemical equilibria
followed by the specific flash definition. The P,T chemical equilibrium flash
can also be activated by the button.
Chemical equilibrium problems are treated in exactly the same way as any other
phase equilibrium problem. There is no need to specify any reaction
mechanism, only to include in the selected components list all the possible
products and reactants you wish to consider. If you do not define both then no
chemical reaction calculation will be possible.
Troubleshooting - chemical reaction

Remember the standard model sets supplied allow for up to three liquid phases
one of them water. As the chemical equilibrium model is limited to one liquid
phase the software will only consider the first two phases, GAS and LIQUID1.
You may therefore see a warning message
Chemical equilibrium at fixed P and T:
*** WARNING -30131 ***
More than 2 fluid phases defined - first 2 used.
This may be ignored provided that the first two phases (GAS and LIQUID1) are
the ones you wish to use.
If you are looking at a problem with pure solid phases the data for components in
the pure solid phases should be taken from INFOCOND, rather than
INFODATA. In this case the component will be assumed to be a solid and the
phase types/names will not need to be adjusted to account for these solid phases.
The components that appear in the mixed vapour and /or liquid phases should
then be taken from one of the fluid component databanks as usual.

Units
Introduction
A significant proportion of the apparent errors and problems reported for
Multiflash can be tracked down to a mismatch between the units the user thinks
he/she is using and those currently set in the software. The importance of
matching units cannot be stressed too much. Having said that, what units are
available for you to select?
Internally all Multiflash calculations are carried out in SI units. This cannot be
changed. The default input and output units are also SI. Unless you change the
units any numerical input values for any property will be assumed to be in SI.
The input amounts for any calculation are total amounts. The output defaults are
that individual compositions of any phase are given as fractions but the amount
of the phase is the total amount.
Working units
Internally all Multiflash calculations are carried out in SI units. This cannot be
changed.
Default units
The default input and output units are also SI. Unless you change the units any
numerical input values for any property will be assumed to be in SI.
The input amounts for any calculation are total amounts. They may be set as
percentages in the PVT Analysis Form or the Inhibitor Calculator, but they will
be converted to absolute amounts for calculation or display in the Composition
drop down table. The output defaults are that individual compositions of any
phase are given as fractions but the amount of the phase is the total amount.
Changing units
You may change any of the input or output units. In Multiflash 3.3 units can be
altered as a "block" by choosing "All Metric" or "All British". Units for all
properties will be reset to:
All Metric;
mole, DegC, bar,m3/mol, J/mol, J/mol/K, cP, W/m/K, N/m, m2/2
User Guide for Multiflash for Windows Units 135

All British;
lbmol, DegF, psi, ft3/lbmol, BTU/lbmol, BTU/lbmol/F, cP, BTU/hr/ft/F,
dyne/cm, cm2/s
Of copursde, you can change any of the property units individually. Changing
units can be done in a variety of ways
Changing units interactively

The units may be changed for any property at any point. To change the units
Select Select from the menu bar, then
Select Units
or
Click on the Select input and output units button

or activate the Units button in any appropriate dialogue box.
Any of these actions will activate the Tab control for units selection:
To view the currently selected units for any property click on the corresponding
tab. To change the input units for any property click on the option button next to
your choice of unit in the Input unit column. This button will then be set. Do
the same in the Output unit column to change the output units for that property.
The input and output units do not have to match.
The output composition may be changed from fractions to total amounts on the
Amounts tab. It is not possible to change the input composition to fractions.
This Tab control panel for units selection can be also accessed by clicking the
Units button from a dialog box such as Phase envelope, Tolerance calculation,
defining Petroleum fractions , Pure Component Data, Match Dew Point, Match
Bubble Point and Tables.
Changing units in a problem setup file

You can define your input and output units as part of a problem setup file. In
fact we would recommend that you do define input units where you wish to
include the numerical values for any of the input conditions in the file to avoid
136 Units User Guide for Multiflash for Windows

any possible mismatch with the units currently defined under Windows when the
setup file is loaded.
The command for defining units is of the form:
inputunits property_name units_name;
More than one set of input units may be defined at any time. You must finish
the command with ; as an end marker. e.g.
inputunits amounts kg temperature degF;
Output units are defined in a similar manner after the command
outputunits. If you use the command
units
both input and output units can be defined at the same time.
If you save a problem set up in Windows the unit definition will also be saved as
part of the problem setup file.
Changing the default input and output units

MFCONFIG.DAT may be If most, or all, of your calculations are carried out in one set of units, but not SI,
used to preset other defaults then you may wish to change the default units. This may be done by specifying
such as the level of physical the changes in a file called MFCONFIG.DAT. If no such file exists in your
property output. installation directory then create one. In this file set any defaults, such as input
and output units, using the commands described (Changing units in a problem
setup file on page 153). This file is checked as Multiflash is started and any
commands contained in it are activated.
Troubleshooting - units
The only problems we have encountered with units arise from a mismatch of
those currently set in the software and those assumed by the user. It is always
worth checking the units are what you expect if you run into problems.
User Guide for Multiflash for Windows Units 137

Output
Introduction
The output from Multiflash appears in the results window which occupies the
bulk of the main window. The output is also written automatically to a log file,
called MFLASH.LOG. It is also possible to print results or to write them to
another file of your choice. How you do this will be discussed in Writing the
results to a file on page 156.
The results window.

As soon as Multiflash is activated the banner appears in the results window.
******************************************************
******************************************************
MULTIFLASH Version 3.3.47 November 2003
Serial number: 0
For internal use only
Copyright(C) Infochem Computer Services Ltd, 1989-2003
******************************************************
******************************************************
Run on: 30 November 2003 at 09:53
Databank configuration file:
C:\Program Files\Infochem\MF33
------------------------------------------------------
Multiflash output will be recorded on the following
file:C:\Program Files\Infochem\MF33\mflash.log
The banner contains information on the serial number for your copy of
Multiflash; the time and date of the current run for documentary purposes and
information on the path used to search for the configuration file
AYCONFIG.DAT. It also gives the pathname for the log file and shows the
contents of the MFCONFIG.DAT file if you have one.
Problem setup files, loaded through the File/Load Problem Setup menu and the
contents of model configuration files are also displayed in this window.
Before the output from each calculation, the results window displays a separator
followed by a comment line to reflect the command. Examples would be
User Guide for Multiflash for Windows Output 139

Dew point at fixed T:
to indicate that you have activated a dew point calculation at fixed temperature
flash, or
Clear current problem setup
to confirm that you have cleared the previous problem using the File/Clear
Problem Setup menu option.
If you use the Tools/Command option to send a command this will also be
displayed in full in the results window, after the comment Command line, e.g.
Command line: show pvt;
All the results from the Multiflash calculation will be sent to the results window,
including comments, warning and error messages. This output will be
considered in detail later.
There is a limit of 32,000 characters that can be stored in the results window.
Earlier results will be overwritten once this limit is reached. Similarly if you
choose to write the output to a file of your own choice only the contents of the
results window will be stored. However, all results will be written to
MFLASH.LOG unless the results from any set of calculations (defined in a
problem setup file) exceeds 32,000 characters.
If all the output is not visible in the results window then it can be viewed by
scrolling vertically or horizontally. It is also possible to extend the size of the
window by dragging.
Font
The default font for displaying results in the output window is Lucida Console,
10 pt. This can be changed by the user from the Tools/(Output Window)
menu option.
The possible fonts available will depend on the particualr PC installation. When
changing fonts we recommend that you always choose a mono-spaced font so
that the column output is retained.
Writing the results to a file

As well as being sent to the screen in the results window the output is also sent
to a log file which may be examined later. The default log file is called
MFLASH.LOG and this will be overwritten the next time you load Multiflash
unless you rename it. To retain the log file for documentary purposes either
140 Output User Guide for Multiflash for Windows

rename MFLASH.LOG before running Multiflash again or send the contents of
the results window to a specified file.
This may be done by choosing the File/Save Results menu option.
You will see a message box which allows you to write the entire output window
to file.
If you have previously highlighted a section of the output then the message box
offers the option of writing the selected text to file.
A dialogue box allows you to choose the file name and directory. The
convention is that the extension for output files is .out, but you may alter this if
you wish.
Printing the output

You can print the output from your calculations by
Selecting File from the menu bar, then
Selecting Print Results
or
Clicking on the Print results button,

The Print window allows you to configure your printer as in any Windows
application.
If you only wish to print part of the output you should select the relevant section
by highlighting it with the cursor. You then select print results as above.
Alternatively you can cut or copy the relevant sections and paste them to another
application, such as Word using the Edit menu.
Calculation output
Calculation output will vary slightly depending on the type of calculation and the
level of physical property output specified but will be in the style
The first line of output reports the temperature and pressure. These may be either
the input conditions or the values calculated from the flash.
This is followed by three messages:
No. Phases reports the number of phases that have been found at the particular
temperature and pressure.
CONVERGED means that the calculation has been completed successfully. If a
solution has not been found then error messages would be produced and any
results would be labelled FAILED. If a warning has been generated then you
may see the message ?UNCONVERGED. In the latter two cases the error or
warning messages should be read carefully to assess the problem.
Multiflash can only check for STABLE means that no further phases (out of the list provided) will form.
the stability of a solution with Sometimes a solution may be labelled as UNSTABLE, meaning that further
respect to the formation of phases would form if more phases were allowed for in the problem setup. An
another phase of a type example might be if only vapour and one liquid phase are specified but in fact
already specified. For the true solution is vapour-liquid-liquid. If you want to look for the extra phase
example, if you have only then you must include an additional phase descriptor in your model definition.
defined two liquid phases the If, however, you are at very low temperatures you may be looking at a
possible formation of a metastable solution and wish to retain only the number of phase descriptors
vapour cannot be checked already defined. The results of a hydrate nucleation calculation will always be
labelled unstable. It is also possible to see the message MARGINALLY
STABLE. This means that, although the solution is stable, changing the
conditions slightly might result in the formation or disappearance of a phase, for
example near the critical point.
The remaining output depends on the setting for the physical property output
level. For each phase the phase name is given underneath to identify it uniquely.
The previous example shows output from the default setting.
The column labelled OVERALL gives the total mixture properties (where
applicable). The default composition units are moles. The compositions shown
are actually mole fractions, but the Phase totals are in moles. If mass-based
output units for amounts are chosen the compositions displayed are mass

fractions and the totals are in the selected mass units. If you want the output in
absolute amounts not fractions you set this on the Amounts tab of the Select
Units option.
Z is the compressibility factor calculated from the same model as used to
calculate fugacity coefficients (K-values). The average molecular weight has
units of g/mol. V/Dens. is the molar or specific density or volume calculated
from the volumetric model in the selected density/volume output units. U, H, S
and G are the internal energy, enthalpy, entropy and Gibbs energy of each phase.
If you have extended the physical property output then the additional properties
will be listed below these, e.g.
Cp (J/mol/K) heat capacity at fixed pressure
Cv (J/mol/K ) heat capacity at fixed volume
Speed sound (m/s) thermodynamic speed of sound
Visc.(Pas ) viscosity
Th.C.(W/m/K ) Thermal conductivity
ST (N/m) surface tension
If you have selected the thermal properties relative to the elements these are
labelled as below:
Helm(J/mol ) enthalpy
Selm(J/mol/K ) entropy
Uelm(J/mol ) internal energy
Gelm(J/mol ) Gibbs energy
If the fugacity coefficients and activity coefficients have been selected the
coefficients for each component in each phase are listed as follows:
COMPONENT OVERALL PHASE1 PHASE2

GAS LIQUID1
fug. coeff. fug. coeff.
BUTANE .86231 1.2403
PENTANE .79165 .56033
Activity coefficients may not be a valid property for all components in all
phases. This will depend on the component and the model. If the property is not
valid N/A will be displayed.
Finally, values for diffusion coefficients are displayed. If the model definition
has been set to include diffusivity then the output will automatically include
diffusion coefficients. If Diffusivity has been set for property output but not
included in the Model Set definition then the property label will appear but not
the numeroc values.
PHASE1
GAS
Diffusion coefficient (m2/s )
ACETONE WATER
ACETONE 8.00080E-06 1.86663E-05
WATER 1.86663E-05 4.29283E-05
PHASE2
LIQUID1
Diffusion coefficient (m2/s )
ACETONE WATER
ACETONE 7.15035E-09 2.96215E-09
WATER 2.96215E-09 4.55884E-09

Output to Excel
The calculation output to the main Window has been re-formatted. The
appearance remains the same but output can now be copied as a block and pasted
to Excel, where the columns will be recognised. New facilities also allow the
user to copy a single column from Excel, e.g. the liquid phase composition from
a flash, and use this as input to another flash calculation in Windows by pasting
the amounts in the Composition drop down table.
Phase envelope output

The phase envelope calculator produces plots of the chosen phase boundaries in
the Phase Diagram window. The default is to plot each phase boundary with a
solid line, but as a different colour, and the legends are the phase descriptor plus
the fraction of that phase requested, with V/L for the phase envelope generated
by V/L Autoplot.
The range of points calculated or plotted can be controlled by the Phase
Envelope dialogue box and the plot customised, e.g. legends and line types
changed as discussed in section Customising the phase envelope plot on page
145. Phase envelope plots can be exported in several formats, including .wmf,
.bmp and .jpeg. They can also be directly written to Excel, see Write to Excel
on page 146.
Errors and warning messages

It is not practical to provide a full list of potential error and warning messages.
When they occur an error number will be reported in the results window,
followed by a single line description of the error, e.g.
*** ERROR 344 ***
For further information you can type HELP followed by the error number in the
Tools/Command dialogue box, e.g.
Help 344;
Further information will then be printed in the results window.
*** ERROR 344 ***
Module: Multiflash command processor
Subprogram: MFCALC
Error: 344
The call of the Multiflash flash routine has
returned with an error state. Results are invalid.

The information on the module in which the error occurred and the subprogram
name is intended for use by Infochem technical support.
A full list of the Multiflash error codes is now available through the HELP
function.
Warning messages should be checked carefully. In many cases they may be
ignored if the cause is understood.
Errors are usually associated with Multiflash output indicating a failure to find a
solution or that the results may be invalid.
Displaying status for current settings

Show options in the Tools menu allow the user to check the status of most of the
Multiflash options. The Show options are probably self-descriptive but they are
summarised in the table.
Show options
Amounts Displays the amount of each component in the stream
BIP databank The name of the active BIP bank for the problem e.g.
oilandgas4
Black Oil Analysis Details of the input to the Black Oil Analysis PVT
form
Characterisation The correlations used to predict physical properties of
method the petroleum fractions e.g. INFOCHAR
TBSOEREIDE
Components List of components in the input stream
Models List of the model set
Phase descriptors Phase descriptor names for the phases to be included
in calculation
Problem Full definition of the current problem
Pure Component The pure component databank current at the time of
Databank request
PVT Analysis Description of the settings in the PVT Lab Analysis
form
Results Repetition of the results from the last calculation
Stream Types Displays number and names of active streams
For brevity much of the output from the show option will be in keyword form.
For instance, under Characterisation method, TBSOEREIDE is the name of the
correlation used for calculating the boiling point of a petroleum fraction. The
alternative would be TBAPI.
The output for Show Models will depend on whether the model has been set
interactively or loaded in as part of a problem file. In the latter case the
thermodynamic model may only be referred to as MEOS. To obtain more
information you would still have to use the Tools/Command option and type in
Show model meos;
If the model has been defined interactively more detail is given at the initial
Show Models stage e.g. MPR is the Peng-Robinson model.

Troubleshooting - output
Problems relating to the flash calculations, which may be reflected in the output,
have been dealt with earlier. However, some problems directly related to the
output may be worth mentioning.
The output does not include everything

expected
Remember that there is a limit of 32,000 characters for the results window. If
your output exceeds this then, as the last 32,000 characters are retained, earlier
results may be overwritten. You can of course cut and paste results to another
document when you reach the limit or take the results from the log file.
The output may not contain all the properties expected. This may be because
they have not been selected, see Property output in Multiflash on page 146 or
because a model for the property has not been defined. If you are not using a
model configuration file or model set to define your model you must remember
to include transport property models if you wish to obtain transport property
output. This is particularly important when creating PVT files for PIPESIM or
TAB files for OLGA.
Phase labelling
The phase names attached to each of the possible phases which may form
enables you to keep track of the phase output. One case where some confusion
may arise is for dense phases, where it is not possible to decide unambiguously
whether the dense fluid is a liquid or a gas. In this case the phase name may
change with slight alterations in conditions. This does not affect the correctness
of the results or phase properties, it is only the label attached to the phase that is
ambiguous.
Phase envelope
This facility is unusual in its ability to plot multiple phase lines. The phase
envelope output is designed so that you can build up complex phase diagrams by
adding different phase boundaries. If you forget to clear the plot or clear the
problem setup this may lead to the plot from a new problem being superimposed
on that from an earlier plot. In this case either Delete the individual phase
boundaries from the earlier plot using the Options facility or Clear the whole plot
and start again.
Fonts
Occasionally users have reported not being able to read the output in the results
window. This appears to be the result of particular PC installations where the
font type or size has been re-set to choices that are incompatible with our
display. They can be set to acceptable choices, see Font on page 140.

Interfaces with other programs
Introduction
In addition to using Multiflash to do stand-alone calculations it is possible to
create property data files for use by other application programs. Multiflash can
currently produce Pipesim PVT files and files for input to OLGA. The faciltiy to
produce HTFS Process Simulator Interface Files (PSF) has been removed from
Multiflash 3.3.
Pipesim PVT files

Pipesim is a general purpose simulator for modelling fluid flow in oil and gas
wells, flowlines and pipeline systems. It is a product of Schlumberger
Information Systems.
Multiflash can produce a PVT data file for use by Pipesim. The file contains all
the physical property information required by Pipesim. It consists of a series of
flash calculations on a grid of pressure and temperature values. The information
stored includes the stream composition and, for each grid point: liquid volume
fraction, watercut volume fraction, liquid density, gas density, gas
compressibility factor, gas molecular weight, liquid viscosity, total enthalpy,
total entropy, liquid heat capacity, gas heat capacity and liquid surface tension.
For a complete definition of PVT files see the Pipesim manual.
To generate the file:
Define the models (which must include models for surface tension and
viscosity) and the mixture (components and composition) as usual
Select Table in the menu bar, then
Select PIPESIM
Fill in the subsequent dialogue box. with the pressure and temperature grid
points and the name of the output file. The recommended extension is .PVT.
User Guide for Multiflash for Windows Interfaces with other programs 147
Click on Calculate table
Assuming there are no problems the output will go directly to the .PVT file, it
will not be sent to the results window. In the results window you will see the
message
Pipesim table generation:
table pipesim "Pipe6.pvt" pressures 1e5 5e5 10e5;
temperatures 350 400 450;
title "Output for pipe 6";
*** Generating Pipesim table - please wait ***
*** Table successfully generated ***
If any of the input is unacceptable, such as specifying negative pressures or
absolute temperatures or if Multiflash cannot solve the flash calculation at any
grid point then a warning message will appear
.
It should be noted that any user BIPs specified by the user in Multiflash will not
be carried forward to the .pvt file. However, in line with recent changes to
PIPESIM .pvt files written with Multiflash will contain information on the
version of OILANDGAS and the viscosity model used.
OLGA
OLGA is a general purpose transient simulator for modelling fluid flow in
flowlines and pipeline systems. It is a product licensed by Scandpower A/S.
148 Interfaces with other programs User Guide for Multiflash for Windows
Multiflash can produce a PVT data file for use by OLGA. The file contains all
the physical property information required by OLGA. It consists of a series of
flash calculations on a grid of pressure and temperature values. The information
stored includes all the properties required by OLGA for either two-phase or
three-phase problems as set out in Scandpower Technical Note No. 1.
To generate the file:
Define the models (which must include models for surface tension, thermal
conductivity and viscosity) and the mixture (components and composition) as
usual
Select Table in the menu bar, then
Select OLGA
Fill in the subsequent dialogue box. with the pressure and temperature
grid points and the name of the output file. The recognised suffix for
OLGA tables is .tab. This will be allocated automatically if you use the
Browse facilty to identify a suitable directory and save the file from
there. Alternatively you can typ in the .tab suffix as aprt of the file
name. If you want the file saved in a particular directory you must
enter the full pathname, otherwise the file will be saved in the current
default directory. OLGA requires a File id (strating with a letter not a
number). If you don't provide one Multiflash will assign one
automatically.
Click on Calculate table

Assuming there are no problems the output will go directly to the .named file, it
will not be sent to the results window. In the results window you will see the
message
Olga table written to file: oil.tab
If any of the input is unacceptable, such as specifying negative pressures or
absolute temperatures or if Multiflash cannot solve the flash calculation at any
grid point then a warning message will appear. This may be an indication that
you have incorrect input
or the calculation routines may fail and the error may be
User Guide for Multiflash for Windows Interfaces with other programs 149
.
CAPE-OPEN Interface
Infochem has been an active participant in developing and testing the CO
standards. The Multiflash CO modules implement version 1.0 of the standard
and support the ThermoSystem and Property Package interfaces. The interface
has been tested for interoperability with Aspen+, gPROMS and HYSYS.
To generate a file from Multiflash that can be read by the Multiflash CAPE-
OPEN module simple set up the problem in Windows as usual. Instead of
saving the Problem Set-up you use the file option for Export CO Property
Package. A separate manual for the CAPE-OPEN Interface is provided on the
Multiflash CD-ROM.
150 Interfaces with other programs User Guide for Multiflash for Windows
Help
Introduction
Help is provided in various ways:
The printed User Guide
On-line Help
Website support
Technical support
User Guide
The User Guide explains how to use Multiflash in detail and contains several
case studies and a simple tutorial, plus an Appendix listing useful commands
which can be used through Tools/Command in the menu.
On-line help
The on-line help will be familiar to regular users of Windows applications. It is
accessed through the HELP menu
Help Topics provides access to the Contents, Index and Search

facilities for Multiflash Help. The Multiflash Error Codes detail the meaning
of the Error and Warning codes. This will be a familiar facility for users of the
Excel interface but new to Help in Multiflash for Windows.
User Guide for Multiflash for Windows Help 151

Selecting any active topic will bring up the related help text.
Related topics are further sub-headings and more help is displayed by selecting
any of these.
Some of the help text may be displayed in green. If this is underlined with a
solid line, clicking on the text will allow you to jump to another help screen
related to the text. If the text is underlined with a dotted line, clicking on it will
result in a pop-up box containing a glossary definition or a margin note.
Selecting Search, either from the HELP menu or via the Search button in the
on-line help window allows you to specify a particular topic you are interested
in, either by typing in a description or selecting from the list displayed.
152 Help User Guide for Multiflash for Windows

Clicking on the Display button or double clicking on the topic allows you to
move to the related help text.
Selecting Using Help starts up the Windows help system, with which you can
learn how to use the Windows help system.
Methods of accessing on-line help are based on standard Windows techniques.
However, the 'About Multiflash ....' section is particularly useful when trying to
identify the causes of any problems which may arise when implementing or
running the software.
User Guide for Multiflash for Windows Help 153

Your serial number together with the version numbers for the .dll (here 3.2.27)
and the interface (here 3.2.18) help us to uniquely identify the software you are
using. If you are reporting problems to us, particularly if we are unable to
reproduce them, we may ask you for this information.
The lower text box shows the path for the configuration and log files. The
information contained in the AYCONFIG.dat specified is used to identify where
to find databanks and error message files. You should check that this
AYCONFIG.dat is correct if you experience problems in accessing data or
messages.
The .log file is the file which automatically records the input and output
information for any run.
If you do not set up an MFCONFIG.dat file, which can be used configure
Multiflash options such as default units, then the path for this will not be shown.
Website support
We now have an additional level of help. Our website, http://infochemuk.com
can now be used to report bugs found in Multiflash and to see any
bugs/problems we or other users have found. Where these have been fixed we
will tell you which release version does or will contain the corrections. If we are
still considering how to tackle the problem but know of a work around we will
advise you of our suggestions. We also hope in the near future to allow you to
download updates from our website to pick up changes to the software. At the
moment this is limited to the front-end and all the relevant drivers for the
dongles.
Technical support
If you need further assistance contact us at:
Infochem Computer Services Ltd.
13 Swan Court
9 Tanner Street
London SE1 3LE
UK
Telephone: +44 (0)20 7357 0800
Fax:+44 (0)20 7407 3927
e-mail: support@infochemuk.com
154 Help User Guide for Multiflash for Windows

Case studies - Pure component
data
Introduction
Although the primary purpose of Multiflash is to calculate the thermodynamic
properties of mixtures there may be occasions when you simply want to know
the properties of a pure component, particularly those from a particular data
source. This is quite simple.
Physical properties of a pure component

If you want the physical properties of a pure component, for example octane,
over a range of temperatures you must either:
Define the problem in Multiflash
Load an existing problem setup file into Multiflash
Edit an existing problem setup file and load it into Multiflash
Write a new problem setup file and load it into Multiflash
If you want to know the stored values for the temperature independent properties
or the correlation coefficients of a temperature dependent property you must
choose Pure Component Data from the Tools option from the menu bar
described earlier, see Viewing and editing pure component data. on page 92.
Defining the problem interactively

Having successfully loaded Multiflash, choose a suitable model for the problem.
If you wish to obtain the properties from the data source correlations then you
must use the ideal gas and ideal solution models. This is the Ideal Mixing
model set. With this option all properties will be taken from the databank
correlation except liquid Cp which is calculated from the vapour phase model
and the enthalpy of vaporisation. (If any other model set is defined then only the
pure component properties needed for that model set will be taken from the
bank. Other properties will be calculated using the model set definitions which
include models for the transport properties).
To specify the Ideal Mixing model set:
Select Select from the menu, then
Select Model set, followed by
User Guide for Multiflash for Windows Case studies - Pure component data 155
Selecting Ideal Mixing from the Activity Model selection. Choose the gas
phase model as Perfect gas. The recommended and default model for transport
properties is Mixing rules
You will see a message to say that the Ideal Mixing model set has been
successfully defined.
Click on OK
For more information on models see Models on page 39.
Specify the pure component of interest in this case octane
Click on the Select Component button,

or
Select Select then Select Component from the menu bar.
then specify the data source and component in the Select Components dialogue
box
The data source is set by:

Clicking on the arrow to the right of the data source text box and
Clicking on the data source of interest, in this case INFODATA, the Infochem
Fluids databank
The component is specified by either:
Selecting the Name option button, typing the component name in the
enter name box, then pressing the enter key or clicking on Add
Selecting the All components button, scrolling through the list of
components which will appear in the dialogue box and either selecting octane,
then clicking on Add or Double clicking on octane
156 Case studies - Pure component data User Guide for Multiflash for Windows
or
Selecting the formula option button, typing C8H18 in the text box,
clicking on Search, selecting octane in the Components in databank text
box, then clicking on Add or double clicking on octane
Specifying the physical property output level.
If you are interested in pure component data you will probably want to output all
available physical property data except thermal property data relative to
elements.
Select Select in the menu bar and then select Property output.
In the resulting dialogue box, the first two are the default options for output of
thermodynamic data, click Heat capacity/Speed of Sound and the set of
transport property data and finally click on OK.
Enter the composition for the stream.
In this case where we have a pure component the composition is not important
provided it is a positive value.
In the main window, click on composition, then type 1.0 in the right-hand
column of the table next to octane.
To obtain the properties of liquid octane on the saturation line you must carry
out a bubble point flash calculation at a specified temperature.
Specify the temperature and the flash calculation
Type the first temperature, say 250K, in the text box next to temperature in the
input conditions section
Click on the Bubble point at fixed temperature button , or select Calculate

from the menu bar, then select Bubble and Dew point flashes and finally
select T, Bubble point flash.
The reported pressure is the saturated vapour pressure at 250K, the other
properties are listed below the phase equilibrium output. As we are dealing with
a pure component exactly the same results would be obtained if we had specified
a dew point flash at the same temperature.
The next temperature should be entered in the text box in the Conditions section
and the bubble point flash repeated at this temperature.
Producing a problem setup file

You can carry out the same calculation, or series of calculations using a problem
setup file. We have provided an setup file for calculating the physical properties
of pure octane over a temperature range from 250 to 500K at 50K intervals. We
hope that the commands used are self explanatory. (Simply edit this file if you
wish to obtain pure component data for another compound or properties over a
different range of temperatures). You can also overwrite the default choice of
data source.
To write a problem setup file yourself, use the file shown as an example or save
the problem you have specified interactively
Obtaining properties from Pure component Data

option
Although the standard output from Multiflash does not contain any of the
constant properties, or indeed the correlation coefficients for the temperature
dependent properties, it is possible to obtain these.
Select the components you are interested in, for example octane, as described
above. Select Tools from the menu bar, followed by selecting Pure
Component data, the following dialogue box will then be activated.
As we are dealing with a single component this will be the only choice available
so making sure it is highlighted. Select a property in the list of Select property,
click on Edit to view or change the property. You can also print the properties
in the results window by clicking Write to Output. This output can then can be
saved or copied into other files.
show components "OCTANE" data ;
1 OCTANE
MOLECULARWEIGHT 114.23 g/mol
TCRIT 569.32 K
PCRIT 2.49700E+06 Pa
VCRIT 4.86296E-04 m3/mol
ACENTRICFACTOR .39690
ACENT2
TBOIL 398.82 K
HFORMATION -2.08447E+05 J/mol
SSTANDARD 466.73 J/mol/K
TMELT 216.37 K
HMELT 20740. J/mol
SMELT J/mol/K
CPMELT 50.008 J/mol/K
VMELT 1.96794E-05 m3/mol
RUNIQUAC 5.8486
QUNIQUAC 4.9360
THLWATER K
VHLWATER m3/mol
DIPOLEMOMENT .00000 debye
PARACHOR 351.40 (dyn cm-1)1/4 cm3/mol
RADGYR 4.68040E-10 m
HOCASS .00000
GFORMATION 16000. J/mol
TTRIPLE 216.38 K
PTRIPLE 2.1083 Pa
HCOMBUSTION -5.07415E+06 J/mol
V25 1.63374E-04 m3/mol
SOLUPAR 15448. (J/m3)1/2
SOLIDSOLUPAR (J/m3)1/2
ZCRIT .25877
REFRACTINDEX 1.3951
TFLASH 286.00 K
TAUTO 479.00 K
FLAMLOWER .80000 vol %
FLAMUPPER 6.5000 vol %
SPGRAVITY .70662
EXPANSIVITY 1/K
OMASCALE
OMBSCALE
CNUMBER
REFVISCOSITY Pas
HYDOC
HYD1
HYD2
HYD3
ASSBETA
ASSEPSILON J/m
ASSGAMMA
ASSDELTA 1/K
ASSFF
ASSAC J m3/(mol)2
ASSBC m3/mol
ASSKAPPA
SAFTKAPPA
SAFTEPSILON K
SAFTGAMMA
SAFTFF
SAFTEK 242.78 K
SAFTSIGMA 3.83730E-10 m
SAFTLAMBDA
SAFTM 3.8176 1/mol
EOSC
LJEVISC J/K
LJBVISC m
TYPE 1.0000
COMPREFNO 93.000
CPIDEAL 1.0000 -32384. -3721.4 4.0000
76.000 290.00 -1.3945 5.6330
-5.7710 .00000 . 00000 10000.
PSAT 3.0000 -7.9121 1.3801 -3.804
-4.5013 260.00 568.95
HVAP 1.0000 54909. .37750 .00000
.00000 .00000 .00000 568.38
LDENS 1.0000 2032.5 5407.6 .00000
568.38
LVISC 2.0000 -20.463 1497.4 1.3790
.00000 .00000 216.38 398.83
VVISC 1.0000 3.11910E-08 .92925 55.092
.00000 216.38 1000.0
LTHCOND 5.0000 .21560 -2.94830E-04 .00000
.00000 .00000 216.38 398.83
VTHCOND 1.0000 -8758.0 .84480 -2.71210E+10
.00000 339.00 1000.0
STENSION 1.0000 5.27890E-02 1.2323 .00000
.00000 .00000 216.38 568.70
CPLIQUID 5.0000 224.83 -.1866 9.5891E-04
.00000 .00000 216.38 460.00
SDENS 5.0000 8340.9 -3.1515 .00000
.00000 .00000 133.15 216.38
CPSOLID 5.0000 -24.000 1.9472 -8.53600E-03
1.34000E-05 2.09400E-08 20.000 216.37
VIRIALCOEFF 1.0000 2.73900E-04 -5.65219E-04
-3.63347E-04 -1.16166E-05 2.58796E-06
284.38 1500.0
CARNUMBER 000111-65-9
FORMULA C8H18
FAMILYCODE AA
UNIFAC CH3 2 CH2 6
The output includes the pure component constant properties and the coefficients
for the temperature dependent property correlations. The definitions of the pure
component correlations are given in the Multiflash Programmers Guide.
Excel interface
The current version of Multiflash does not include options for tabular output or
for producing graphical output for properties other than phase boundaries. If this
is important to you then we would recommend our Excel interface. For
example, the octane.mfl file was used in conjunction with this interface and
Excel to produce the following output for octane.
Liquid properties on the saturation line
TEMP PRESSURE CP ENTHALPY DENSITY VISCOSITY THCOND SURTEN

K Pa J/mol/K J/mol m3/mol Pas W/m/K N/m
275 427.762009 231.4236 -47031.7 0.00016 0.000694 0.134522 0.023412
300 2038.06 247.738 -41042.5 0.000163 0.000497 0.127151 0.020986
325 7232.42712 264.3592 -34641.4 0.000168 0.000378 0.11978 0.018612

350 20571.971 281.3794 -27819.2 0.000172 0.000302 0.112409 0.016294
375 49413.7029 298.9716 -20563.4 0.000177 0.000249 0.105039 0.014036
400 104100.875 317.4437 -12855.7 0.000183 0.000212 0.09767 0.011846
425 197831.473 337.3402 -4668.02 0.00019 0.000184 0.091032 0.009729
450 346415.385 359.6594 4044.752 0.000198 0.000161 0.085529 0.007696
475 568184.088 386.3901 13359.5 0.000209 0.000141 0.08092 0.00576
500 884336.745 422.1065 23419.76 0.000223 0.000125 0.077028 0.003941
Ideal gas properties at .001Pa
TEMP CP ENTHALPY DENSITY VISCOSITY THCOND
K J/mol/K J/mol m3/mol Pas W/m/K

275 176.527 -4228.471 2286463 4.8E-06 0.010792
300 189.732 350.106 2494323 5.28E-06 0.01224
325 202.750 5256.578 2702183 5.76E-06 0.013937
350 215.530 10485.621 2910044 6.23E-06 0.015937
375 228.032 16030.774 3117904 6.71E-06 0.0181
400 240.223 21884.645 3325764 7.18E-06 0.020388
425 252.077 28039.119 3533624 7.65E-06 0.022801
450 263.577 34485.547 3741485 8.12E-06 0.025336
475 274.711 41214.916 3949345 8.58E-06 0.027994
500 285.473 48217.999 4157205 9.05E-06 0.030772
It is then easy to plot individual properties as a function of temperature or to

compare property values from different data sources.
Case studies - Phase equilibria
Introduction
The main purpose of Multiflash is to determine the phase equilibria and
thermodynamic properties of complex mixtures. The simple tutorial shown
earlier, see Simple Tutorial on page 19. was based on calculating the phase
equilibria of a binary hydrocarbon system. Here we will look at a more complex
hydrocarbon system and the phase equilibria of a polar mixture.
Oil and gas systems

Initially we will look at the phase envelope of a system which contains six
components: methane, ethane, propane, butane, hexane and decane.
As with the pure component data system discussed earlier the case study can be
set up interactively or by using a problem setup file. Only the former will be
discussed in detail, but the setup file, hycbvle.mfl, is provided and may be used
to load models and components or as an example for writing or editing your own
files for handling similar cases.
Specify the model
Any of the equation of state models would be suitable for handling this problem.
We have chosen the advanced version of RKS but very similar results would be
expected using advanced PR, PR or RKS.
Select Select, then
Select Model set from the sub-menu, followed by
Selecting Equations of state from the Select Model set dialogue box and again,
Selecting RKS (Advanced) with the default option for transport property
models.
Finally, click on OK in the message box and Close in the Model set dialogue
box.
Specify the components
User Guide for Multiflash for Windows Case studies - Phase equilibria 163
The INFODATA databank will be the default data source and this is acceptable
for this case study, so we can move directly to specifying the components. You
can activate the Select Components dialogue box by either
Clicking on the select components button

or
Selecting Select from the menu bar and
Selecting Components from the sub-menu
The various methods for selecting or searching for components have been shown
before see Selecting components on page 87. As our current system contains
simple well known compounds they have been selected by
Highlighting the Name option button
Typing the component name in the Enter name text box
and pressing the enter key after the name to load it for Multiflash
or
Clicking on Add to load the component.
Click on Close to load the components
Define the composition
Click on Compositions in the Conditions section, and
Type in the compositions in the drop down table. For our example they are:
Methane 0.45
Ethane 0.20
Propane 0.10
Butane 0.10
Hexane 0.10
Decane 0.05
Calculating the bubble point curve

You can calculate the bubble point curve using a series of flash calculations or
by generating the phase envelope. Individual calculations may be a series of
bubble point calculations at either fixed temperature or fixed pressure.
Technically there is no particular reason to prefer one over the other; for this
particular example we will fix temperature and have our output pressure in bar.
164 Case studies - Phase equilibria User Guide for Multiflash for Windows
To change the pressure units, click on the Select input and output units
button , then in the Tab control click on Pressure and click in the Output
option button box against bar. (You can also change the input units for pressure
if you wish.)
Having specified the model, components, compositions and units,
Enter the first temperature, 250K, in the Conditions section and
Click on the T, Bubble button, .

Repeat the last two steps increasing the temperature by 25K each time. At 375
you still have a stable solution reported but by 400K the solution is reported to
be marginally stable , by 425K the solution will be unstable and at 450K
you will notice a failure message
Bubble point at fixed T:
*** ERROR 20292 ***
*** ERROR 20024 ***
may be no solution.
*** ERROR 344 ***
Investigating the bubble point curve using reduced temperature steps you will
see that at 404K the solution is at the stability limit and the compositions of the
liquid and gas phases are very similar, indicating that we are probably close to
the critical region. You can either investigate this area of the phase envelope
further using P,T flashes or move to calculating the dew point curve to formulate
a view of the phase envelope.
Calculating the dew point curve

As with the bubble point curve, the dew point curve can be calculated from a
series of dew point calculations at either fixed temperature or pressure. Again
we will use dew point calculations at fixed temperature for this example
As with the bubble point curve, start at 275K and calculate the dew point at 25K
intervals using the T, dew point button, .
This time the dew point calculation fails to converge at 475K. Returning to the
last successful convergence at 450K, increase the temperature in 5K steps. This
time the first failure to converge occurs at 470K.
We know that it is probable that the critical point is around 400K so it is a
reasonable assumption that this system has a significant retrograde region.
Check this by repeating the dew point calculation at 450K but this time by using
the fixedphase fraction route and looking for the upper retrograde solution.
To do this:
Click on the fixedphase flash at fixed temperature button,

In the dialogue box which is then activated,
Click on the roll down arrow to the right of Select phase and from the drop
down menu click on GAS. Choose Mole Fraction under Select Basis and enter
a phase fraction of 1.0 in the text box and click on the Upper retrograde type of
solution. This fixedphase flash simulates a dew point calculation.
Click on Do flash.
The calculated dew point pressure is now 114.5 bar for the retrograde region,
whereas for the normal dew point the calculated pressure was 28.18 bar. This
confirms that we have a retrograde region for this system.
To calculate the full dew point curve you therefore need to increase the
temperature at 1K intervals above 460K, using the normal T, dew point flash,
until you meet the first convergence failure, at which point you are just beyond
the cricondenbar. You should now switch to fixedphase fraction flashes at fixed
temperature, set the options as described and reduce the temperature in small
steps. This will define the retrograde dew point curve to 405K.
Phase envelope
The same problem can be investigated more easily using the phase envelope
calculator. Set up the problem as before, but instead of carrying out individual
dew and bubble point calculations
Select Calculate/Phase Envelope or click on the Phase Envelope button
Click on V/L Autoplot and Click on Yes when the message box appears asking
if more points should be calculated. The resulting plot includes the dew and
bubble point lines and the critical point is labelled.
The output in the results window will allow you do identify the critical point
explicitly
53C 402.713 147.11
Adding water to the system

It is quite common in the oil and gas industry to find some water present with
hydrocarbon systems, which will probably form a separate liquid phase. In this
case study we can add water and look for the water dew point line.
To add water to the input stream
With the hydrocarbon case study defined,
Click on the Select component button
In the Select components dialogue box, enter water in the Enter name text box
then press the enter key or click on Add
Click on Close
In the main window, click on composition and in the drop down table enter a
composition for water, say 0.2.
Calculating the water dew point line

If there are more than two liquid phases present then using Multiflash to
calculate the dew point, defining either temperature or pressure, will result in
finding the primary dew point, in this case the hydrocarbon liquid dew point. To
find the dew point for the second liquid phase, in this case water, you must use
the fixed phase fraction flash and look for the temperature or pressure where
there is a zero amount of that phase. Therefore, for the water dew point,
Enter the first temperature in the Conditions section of the main window.
Click on the fixedphase fraction flash at fixed temperature button, .

In the resulting dialogue box, click on the arrow under Select phase and select
water. Under Select basis choose Mole Fraction and enter a phase fraction of
0.0. The normal type of solution should be satisfactory for the water dew
point.
Click on Do flash
Repeat the calculation at increasing temperatures to obtain the water dew point
line.
Alternatively, plot the water dew point line using the Phase Envelope calculator
by selecting the water phase at 0.0 molar phase fraction.
Including a petroleum fraction
The heaviest component in our hydrocarbon stream is decane, but often the
heavier end of oil or gas condensate systems is defined as a petroleum fraction
rather than as a single specified component. Each petroleum fraction will consist
of a mixture of components and the fraction as a whole will be defined in terms
of its molecular weight, density and possibly boiling point, although the first two
properties are the most likely to be reported. Often the heavy end will be
reported as a single fraction, e.g. C7+, although sometimes a more detailed
analysis may be available breaking the heavy end down into several fractions.
Multiflash includes petroleum fraction correlations which may be used to predict
the thermodynamic and transport properties of the fraction based on the data
available, see Calculating petroleum fraction properties on page 118 .
For this case study we will remove decane and water from our stream and
replace decane with a petroleum fraction of molecular weight 234 and specific
gravity 0.838.
To delete components
Assuming the stream definition for the last case study is loaded
Click on Select components button
In the Select Components dialogue box, select water in the list of components
selected for Multiflash, then click on Delete. This will remove water from the
list. Repeat this for decane. You should now be left with methane, ethane,
propane, butane and hexane.
To add the petroleum fraction
In the Select components dialogue box
Click on the arrow to the right of the Data source list box, then select
Petroleum fractions correlations.
In the dialogue box then activated:
Enter C7+ in the Name box, enter 234 for Molecular Weight and enter
0.838 for specific gravity.
Click on Add to include the fraction in the defined stream.
Alternatively you could use the Replace option to replace decane with C7+.
Click on Close
In the main window click on Composition and enter 0.05 for the amount of
C7+.
The petroleum fraction is now included in the stream definition and the phase
envelope calculation may be repeated with the new stream, although the
cricondenbar, cricondentherm and retrograde regions will now be different.
If you only know that the petroleum fraction is C7+ but do not have a reported
MW or specific gravity you can simply fill in 7 as the Carbon number
and Multiflash will determine the properties from a set of standard tables.
Other flash calculations

Many engineering applications involve a wide range of flash calculations, not
just those related to determining the phase envelope. For example, an
isenthalpic flash at fixed pressure can be used to simulate the expansion of a
stream through a valve
Basing this case study on the simple hydrocarbon stream (and model) we first
defined
Methane 0.45
Ethane 0.20
Propane 0.10
Butane 0.10
Hexane 0.10
Decane 0.05
we must initially carry out a P,T flash at the upstream conditions to determine
the enthalpy and then a P,H flash at the exit pressure.
Having loaded the model set and stream information
Enter the upstream temperature, 300K and pressure, 50 bar
Click on the P,T flash button
The calculated total enthalpy is -10932 J/mol
The stream is then throttled isenthalpically to 10 bar, by

Entering the new pressure, 10 bar under Conditions
Entering the calculated enthalpy under Conditions
Clicking on the P,H flash button
The calculated temperature at outlet has dropped to 276.367K.
You can also add the isenthalpic boundary for -10932 J/mol to your phase
envelope.
PVT Analysis
Many users will receive a PVT Analysis of the composition of an oil or gas from
one of the PVT laboratories and wish to use this as input to Multiflash. These
reports follow a fairly standard format and the PVT Lab Analysis form
endeavours to reproduce this to make entering information as easy as possible.
The facility to add or delete components from the generated list is also useful.
The form is discussed in detail in section PVT Analysis on page 110.
The case study we are considering here is based on a problem setup file called
pvt1_new.mfl, which uses the Revised Analysis method.
To enter a PVT Analysis either choose the Select/PVT Lab Input menu option or
click on the icon. The Lab Analysis form will then be displayed.
Initially we will consider a case where you only have a single fluid composition.
First select the datasource for your discrete (i.e. well-defined) pure components.
This can be Infodata or DIPPR and we have chosen Infodata. Next at the top of
the column headed Single fluid choose either mass or mol % as appropriate by
clicking on the down arrow. If your PVT report offers a choice of mole or mass
% it is the mass % that is the experimentally measured data and should be given
preference for separator oils. Next enter the compositions of the discrete
components and the compositions of the petroleum cuts. In the form the
pseudocomponents or single carbon number (SCN) cuts are labelled C6, C7 etc.
In your PVT Laboratory report they may be referred to as hexanes, heptanes etc.,
with the heaviest being labelled as a plus fraction such as C20+ or eicosanes+.
In our example the heaviest SCN is C20.
The overall percentage will be totalled as you enter the compositions. If the final
total is not 100 you will be offered the opportunity to normalise the compositions
when you characterise the fluid.
You can enter further information to define the stream, such as the molecular
weight of the Stock Tank Oil (STO), the total fluid or the heaviest SCN or the
specific gravity of either the heaviest SCN or the STO. We have provided
general advice on when such data should be supplied in Fluid composition on
page 113. As the fluid in question has a heavy end (C6+) which comprises more
than 50% of the stream we should supply this information if possible. We have
therefore entered the molecular weight of the heaviest SCN but if you have the
molecular weight of the total fluid available this may be preferable as this is
again the measured quantity.
We will use the default distribution method, Infoanal2.
You are now ready to define the basis of your characterisation by choosing
where in your existing analysis you want to start redistributing the remaining
fluid into new pseudocomponents and how many pseudocomponents you want
to split this heavy end into. Weve started with the simplest case where we have
chosen to start the split at the heaviest SCN and only allocate one
pseudocomponent. Effectively we are only allocating physical properties to the
existing SCNs. Click on the Do Characterisation button and you will see a
message box such as
followed by a screenshot of the experimental data and the fitted distribution
Click on OK and Close to return to the main window where the new fluid
composition will be reported
Properties of the individual pseudocomponents may be viewed using Tools/Pure

Component Data as usual and further calculations can be carried out on the basis
of this characterisation.
At this point, having successfully characterised the fluid, you can also save the
input as an .mfl file.
A useful way of seeing how changing characterisations alter the results of phase
calculations is to use the phase envelope generator. For instance, plot the phase
envelope of this fluid.
You can investigate various aspects of the characterisation and the sensitivity of
the phase envelope to changing these. For instance you can change the
distribution method to Infoanal1 and re-plot the phase envelope, do this and also
include a n-paraffin distribution by ticking the Estimate Wax Content box. In
the latter case the names and compositions of the fraction custs will differ,
but the phase envelope is not significantly affected.
If you return to the PVT Lab Analysis form and instead of the heaviest SCN
choose total liquid and enter a MW of 68. Do the characterisation and plot the
phase envelope. Then see what the effect is of extending the heaviest SCN to
further fractions, by leaving C20 as the start of the pseudocomponents but
choosing to split it into 5 pseudocomponents. Alternatively you can group the
components by starting the pseudocomponent split at C8 and grouping the plus
fraction into 15 pseudocomponents. You can see that this alters the cricondenbar
but the major effect is on the cricondentherm.
Next, return to the original fluid definition and re-plot the phase envelope, then
in the PVT Analysis form enter a watercut. This is defined in terms of the
volume percentage of the total fluid that is water. In this case choose 3 %. In
the main window plot the new phase envelope and the water phase. boundary.
Finally, return to the original fluid analysis again and this time add a separator
gas. Here we will look at a simple problem where the gas is 100 % methane
added at a GOR of 100 m3/m3. Move to the Liquid + Gas tab and enter 100 next
to methane in the left hand column headed separator gas and in the Recombined
fluid section of the PVT form set the GOR units to m3/m3 and enter 100. Do the
characterisation and return to the main window and plot the new phase envelope.
Black Oil Analysis
The black oil analysis offers the user an opportunity to take a very limited input
specification (known as Black Oil input) for a condensate or oil and from this
generate a normal compositional analysis. Our example is based on the
blackoil.mfl file.
The minimum required input is the gas gravity(relative to air), the STO specific
gravity(relative to water) at 60F and 14.7 psi and the solution GOR. The latter
is the volume of gas produced at surface standard conditions divided by the
volume of oil entering the stock tank at standard conditions. It is often referred
to as Rs.
The remainder of the form is the standard PVT except that you do not provide
molecular weight or specific gravity. You can choose the pseudocomponent
distribution as normal, depending on the final application. In this case the split
is five fractions from C6+. Clicking on Do Characterisation generates the
message that the characerisation has been successfullycompleted in this case
there is no compositional information to generate the compositional plot. The
new composition is echoed in the main window and the phase envelope can be
plotted as before.
Additional data can be added such as the Watson K-factor and/or the Gas
analysis. Plotting the phase envelopes shows the effect of including this data.
Refrigerant mixtures
Several of our customers have used Multiflash to determine the properties of
refrigerants. A number of pure refrigerants were added to our INFODATA
databank several years ago and more recently in our CSM model. We have also
fitted data for a large number of refrigerant mixtures and the BIPs have been
stored in the INFOBIPS databank. For mixtures we have used the RKSA model
to determine the thermodynamic properties of the mixture except for the liquid
volume/density which is calculated using the ideal solution model. This model
combination has been included in a model configuration file called refrig.mfc.
To determine the properties of any refrigerant mixture, first load refrig.mfc using
File/Load problem setup. The refrigerant mixture can then be defined as normal
using Select Components and providing the composition. However, there are
several well defined refrigerant mixtures which have been allocated refrigerant
numbers e.g. R407A. This is a mixture of the pure refrigerants, R32, R125 and
R134A, with a fixed composition (in mass percentages) of 20/40/40. To help
our users we have set up .mfl files defining components/compositions for
R401A
R401B
R401C
R402A
R402B
R404A
R405A
R406A
R407A
R407B
R407C
R407D
R407E
R408A
R409A
R410A
R411A
R411B
R414B
R500
R501
R502
R503
R504
R507A
R508A
R508B
To determine the dew point properties of R407A

Load refrig.mfc
Load R407A.mfl
Select the RKSA model
Specify pressure, e.g. 25 bar or 25e5 Pa
Click on the P, Dew point flash icon or menu item
And the results will be displayed in the results window
Dew point at fixed P:
Polar systems
Multiflash is equally applicable to polar mixtures, although for systems of this
type an activity model, such as Wilson-E, NRTL, UNIQUAC or UNIFAC, plus
binary interaction parameters is usually needed to obtain accurate results. For
the first three models, Multiflash has BIPs available for many binary pairs but
where these are missing you need to supply them. For UNIFAC BIPs are
generated from group structure. Before carrying out phase equilibrium
calculations for polar streams using an activity coefficient model we recommend
that you check the availability of BIPs for your system and look up interaction
parameters for the binary pairs where none are available from INFOBIPs. An
alternative is to fit experimental data to a model used in Multiflash or generate
data from UNIFAC and fit this to the model of your choice. We have provided
sample spreadsheets which allow you to do both using the Excel interface.
Reference: Dechema A good source of experimental data and BIPs is the series of volumes in the
Chemistry Data Series Chemistry Data Series, published by Dechema. The UNIFAC model will
provide estimates of vapour-liquid and liquid-liquid equilibria without the need
Vols I to XIV, Dechema
for BIPs.
Modelling a polar mixture.

Using INFOBIPS
As polar mixtures are usually non-ideal you may have some information on their
phase behaviour and wish to know how best to reproduce this. A simple
example is the acetone/water mixture. The Dechema data series referred to has
several sets of data for this system. We have taken, at random, the data by
Kojima et al, Kagaku Kogaku 32, 149 (1968) and based the example on one
experimental point
Pressure 760 mmHg
Temperature 60.39 degC
x(acetone) 0.4000
y(acetone) 0.8426
We can use Multiflash to see how well different models and different sets of
parameters represent this data. Depending on the relative importance to your
application of accurate temperature or phase composition we can fix P and x and
calculate T and y using a bubble point calculation at fixed P or fix P and T and
calculate x and y with a P,T flash.
We would usually suggest using activity coefficient models to predict phase
behaviour for non-ideal mixtures. If you have BIPs available either from
INFOBIPS or from any other source for any particular activity model then this is
the model you should use.
Specify the mixture by
Clicking on the Select components button
With the Infochem fluids databank as the default data source
Type acetone in the Enter name text box and
Click on the Add button.
Select water in the same way
Click on Close
In the Composition drop-down table enter 0.4 mol of acetone and 0.6 mol of
water.
Set the units (from Select/Units from the menu option or the select units button)
in the Tab control so that the input and output temperatures are in degC and the
pressures in mmHg.
Enter 760 mmHg as the pressure
Select a suitable model
Select in order Select/Model Set/Activity Models/WilsonE to choose the Wilson
E model
To check whether BIPs are stored in INFOBIPs for this mixture go
to Tools/BIPs and when the Show BIP Value box appears click on
Edit.
As you can see BIPs are available.

Click on the P, Bubble point flash button and the model prediction
is a temperature of 61.39 degC and a vapour phase fraction of acetone of
0.82117. This is in reasonable agreement with the experimental results. It may
be possible to improve prediction by over-writing the stored BIPs with those
reported in Dechema for that particular experimental dataset, remembering to
convert to the correct BIP units.
You can repeat the calculation using the UNIFAC model where BIPs
are calculated on the basis of group structure. The corresponding
results are a bubble point temperature of 60.88 degC and a vapour
phase fraction of acetone of 0.82399.
Entering BIPs
You may have a mixture where there are no stored BIPs. Take for
example the system acetone/hexane. If your repeat the earlier
steps to select components, units and models and again look at
the BIPs using the Tools options you will see that for the WilsonE
model no BIPs are available.
Click on the P, Bubble point flash button to see the model prediction using the
default, BIPs = 0.0.
For a mixture of 0.314 mole acetone and 0.618 mole the predicted result is a
bubble point pressure at 40 degC of 311.6 mmHg and a vapour phase fraction of
acetone of 0.3951. The experimental data is 510.8 mmHg with y =0.5485.
However, for this data set Dechema recommends BIPs for acetone/hexane for
the WilsonE model of 1067 and 326.8 cal/mol. Multiflash recognises BIPs in SI
units therefore you must convert these to J/mol, resulting in values of 4460 and
1366 respectively. You enter these values into Multiflash using the Tools /BIPs
from the menu bar.
Select Tools, then select BIPs
In the Show BIP values box highlight WILSONBIP2 and click on Edit
Remember to convert the WilsonBIP2 is the name recognised by Multiflash for BIPs relating to the
units from the Dechema data Wilson E model. This model has two, which may be expressed as constant,
series to the correct input linear or quadratic functions of temperature. The Dechema BIPs are
units for Multiflash temperature independent, i.e. constant. The BIPs are asymmetric and not
interchangeable. It is therefore important that if the BIP values are reported for
acetone as component 1, then the binary pair is entered with acetone as the first
component.
Enter the new BIPs
Click on OK and then on Close in the Show BIP values box.

Click again on the T, bubble point button.
This time the predicted bubble point pressure is 511 mmHg and the gas phase
composition is 0.55417. These give a better prediction of the bubble point
pressure and improvement in the prediction of the gas phase composition of
acetone.
The calculation can be repeated for each of the activity methods, including
UNIFAC. To do this
Select the new model set, this will clear the previous model and BIPs, but
retain the components, compositions and units.
Calculate the P, bubble point without BIPs
Remember NRTL has 3 Enter BIPs, as given in the table below (in J/mol), using the Tools/BIPs option.
constant coefficients, not 2: The bipset names are the model name followed by BIP, e.g. NRTLBIP3,
two asymmetric and one UNIQUACBIP2. BIPs are not required for UNIFAC as they are generated from
symmetric group contributions.
Calculate the bubble point pressure again. with the BIPs.
You should reproduce the following results.
Pressure mmHg y1
Wilson E No BIPs 311.6 0.3951
BIPs: 4460, 1366 511 0.5532
UNIQUAC (VLE) No BIPs 314.1 0.3985

BIPs: -312.8, 2350 517 0.5630
NRTL (VLE) No BIPs 324.1 0..4115

BIPs: 2976, 3052, .52 510 0.5522
UNIFAC (VLE) 514 0.5588
You can see from the results the importance of using interaction parameters for
non-ideal systems. All the calculations were carried out with the ideal model for
the vapour phase. For this sytem using the Virial (HOC) model, or RK for the
vapour phase model does not give significant differences. However, for some
components, such as acetic acid which may dimerise, using the Virial (HOC)
model would be beneficial.
You could also enter different BIPs for this system from the Dechema series and
examine the sensitivity of the results to these variations.
Liquid-liquid equilibria
Many non-ideal polar systems exhibit liquid-liquid equilibria. To model these
systems you must choose an activity model capable of predicting two liquid
phases, the Wilson model cannot do this.
Two suitable models are UNIQUAC LLE and NRTL LLE. The LLE version of
NRTL usually has the parameter set to 0.2 by default. Again to obtain
realistic results you should enter BIPs and we have incorporated BIP data for
over 300 systems into our INFOLLBIPs databank. If you take UNIQUAC or
NRTL parameters taken from the Dechema Chemistry data Series they must be
multiplied by the gas constant (8.314 JK-1mol-1) before being entered.
A typical mixture which exhibits liquid/liquid behaviour is butanol/water
Dechema Chemistry Data Series. Volume V, Part 1, page 236.
If you have set up a problem with only one gas and one liquid phase defined you
may see a warning message above a vapour-liquid or one liquid phase solution.
Flash at fixed P and T:
*** WARNING -20001 ***
Unstable solution, more phases exist.
T =298.25K P=1.00000E+05Pa ? CONVERGED ..UNSTABLE
This instability warning indicates that you should consider looking for another
liquid phase, and define a second phase descriptor for this. Use the Select Model
Sets, or the model configuration files provided for activity methods, to ensure
that two liquid phases are available.
To carry out the case study in Multiflash
Select the UNIQUAC LLE model
Select butanol and water from INFODATA
Set the butanol composition to .5 mol, methanol and water to 0.50.
You can check that BIPs are available using the Tools/BIP
option.
Set the temperature to 298.15K and the pressure to 1e5 Pa.
Carry out a P,T flash.
The mixture will be a single liquid phase.
If you increase the water concentration to 0.7 with 0.3 mole butanol and repeat
the two phase flash you get a liquid-liquid solution.
Vapour-liquid-liquid equilibria
The situation is a little more complicated if you have VLLE. None of the
activity models which can handle VLLE do this well without specific tuning of
the BIPs. The VLE variants of UNIQUAC and NRTL are configured to be used
with GAS and Liquid1 and the LLE variants with Liquid1 and Liquid2. To
calculate VLLE with either you must first "Switch-on" the missing phase. The
only difference is the source of BIPs and we have increased the options by
allowing two BIP databanks to be in force at any time. The LLE model options
are configured to first search INFOLLBIPs, then to supplement any missing
BIPs from INFOBIPs. The VLE variants are configured only to search
INFOBIPs. For VLLE it may therefore be prefferable to use the LLE model
variant. However, it is difficult to make an absolute recommendation, trying
both approaches and assessing the differences might be useful. You can also add
INFOLLBIPS to a VLE variant using Tools/Command and entering
bipdata INFOBIPS INFOLLBIPS;
Azeotropes
You can use Multiflash to identify azeotropes; the temperature and pressure
where the composition of the liquid and gas phase are identical. They can be
investigated by carrying out a series of flash calculations but this is time-
consuming. For binary azeotropes you might wish to consider using the Excel
interface. Below is a plot of gas phase versus liquid phase composition for the
propanol water system using Excel. The azeotrope is clearly identified at a mole
fraction of 0.42 propanol.
Propanol - Water
1
0.9
0.8
0.7
y,propanol
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1
x, propanol
You can vary the pressure or temperature and see the effect on the azeotropic
point, or investigate the effect of adding a third component.
Eutectics
Similarly, you can use Multiflash to determine a eutectic, although again this is
mostly easily seen using an Excel spreadsheet. An example would be a mixture
of benzene and napthalene. In addition to defining a fluid phase model, for
example RKSA, you also need to allocate the freeze-out model to each
component. Using the Multiflash functions in Excel you then carry out a series
of calculations to identify, for a given pressure, the temperature at which solid
benzene and solid naphthalene forms. A plot of the predicted temperature versus
composition for both shows the eutectic point. For the RKSA fkuid phase model
and 1 bar this is predicted to be at 296.3K and a mole fraction of benzene of
.8626. The recently added Regular Solution model could also be used for this
particular mixture. For this fluid phase model the predicted eutectic at 1 bar is
296.4K and .8638 mole fraction of benzene. As the plot below shows the results
for the models are virtually indistinguishable.
Benzene-Naphthalene eutectic
370.00
350.00
330.00
T/K
310.00
290.00
270.00
250.00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x Benzene
Polymers
The inclusion of the PC-SAFT equation of state in Multiflash 3.3 has extended
Multiflash applications to the calculation of the phase behaviour of polymers,
solvents and gases. PC-SAFT is a complex equation and to be able to develop a
robust implementation capable of predicting multiple phases is unusual. Owing
to the high molecular weight, and correspondingly low mole fractions, of
polymers in solution considerable effort has gone into improving the phase
algorithms in Multiflash, but we are aware that further improvements may be
necessary.
Data input
It will not be apparent to the user, but we have re-structured the pure component
databanks to provide a more flexible structure. This will allow storage of the
data required for new models, such as PC-SAFT. Although we have made these
changes in Multiflash 3.3 we have not yet included any data for polymer
components. At present these need to be created using the Multiflash User
Defined component route (Select/Components) and either saved as part of a
complete .mfl file or a partial file containing the polymer data only.
The required input data are:
Critical temperature (TCRIT), critical pressure (PCRIT), acentric factor
(ACENTRICFACTOR),
PC-SAFT parameters (SAFTEK, SAFTSIGMA, SAFTM, SAFTKAPPA,
SAFTEPSILON, SAFTFF)
Ideal gas Cp (CPIDEAL).
Users should note that TCRIT, PCRIT and ACENTRICFACTOR are necessary
to generate starting values for flash calculations but do not affect the computed
results from PC-SAFT. Also SAFTKAPPA, SAFTEPSILON and SAFTFF are
only needed for associating components.
If your system is polydisperse, i.e. has the same polymer but with a range of
molecularweight, then you can enter several polymers with varying properties,
each called by a different name. This is analogous to setting up different
petroleum fractions, although we do not yet have a facility to help the user set up
the data for polymers.
Polymers are not well defined chemical compounds but rather a distribution of
chain molecules of varying molecular weight. In Multiflash, polymers must be
represented by one or more pseudocomponents which must be set up as user-
defined components.
Using PC-SAFT, every pseudocomponent for a given polymer must be assigned
the same values of the pure-compound parameters SAFTSIGMA (in metres, not
ngstrom units) and SAFTEK. In addition, the SAFTM parameter must be
specified. This is normally quoted as a ratio to the molecular weight, so it has to
be calculated for each polymer pseudocomponent knowing the molecular weight.
For polystyrene, for example, Gross and Sadowski give the ratio as 0.019, so for
a polystyrene pseudocomponent of molecular weight 100000, the SAFTM
parameter should be set to 1000000.019=1900, etc.
Our example polymer.mfl describes a simple binary of polystyrene plus butane.
The required properties of polystyrene are included in the input file, as are the
pure component SAFT parameters for butane. Load the input file in the normal
way and carry out a P,T flash at the input conditions supplied. The results show
a liquid-liquid split as expected.
You can also carry other flashes, such as a bubble point calculation
PC-SAFT has two interaction parameters, no interaction parameters for PC-

SAFT are stored , both are set to zero by default. As with all Multiflash models it
is possible for the user to enter BIPs through the Tools/BIP command or as part
of the input file. Similarly to CPA, in most cases it is the parameter, SAFTBIP
that is adjusted. As the polymer is in volatile, changing the BIP may affect the
phase distribution and phase compositions more than the bubble point prediction.
The result of altering the SAFTBIP from 0.0 to .05 is shown below
A slightly more complex system, polymer2.mfl, shows the unusual ability of

Multiflash to deal with complex systems. In this example pentane replaces
Butane as a solvent and we introduce the styrene monomer as a fourth
component. In this case a bubble point calculation predicts the presence of four
phases.
The series of papers by Sadowski et al, detailed in the "Models and Physical
Properties Guide, are a useful source of input parameters for PC-SAFT for
several polymers.
Until the advent of PC-SAFT, Flory-Huggins was sometimes used for polymer
calculations. This is still possible but not recommended. To apply the Flory
Huggins model, in addition to the critical parameters required by the Multiflash
algorithms the additional data needed are: vapour pressure (PSAT), saturated
liquid density (LDENS), solubility parameter (SOLUPAR) and molar volume at
25C (V25).
Estimated properties have been included in the file polymer3.mfl for polystyrene
and the predicted bubble point for the polystyrene-butane binary shown below.
Case studies - Hydrate
dissociation, formation and
inhibition
Introduction
This section is only applicable if your copy of Multiflash includes the hydrates
option.
Natural gas hydrates are solid ice-like compounds of water and the light
components of natural gas. Also, some heavier hydrocarbons found in gas
condensates and oils are now known to form hydrates if smaller molecules such
as methane or nitrogen are present to stabilise the structure. Hydrates may form
at temperatures above the ice point and are therefore a serious concern in oil and
gas processing operations. The phase behaviour of systems involving hydrates
can be very complex because up to seven phases must normally be considered.
The behaviour is particularly complex if there is significant mutual solubility
between phases, e.g. when inhibitors or CO2 are present. Multiflash offers a
powerful set of thermodynamic models and calculation techniques for modelling
gas hydrates.
The models used in Multiflash for hydrates and hydrate inhibition have been
briefly described, see Hydrate model on page 55 or our separate guide to
models and physical properties.. Components known to form hydrates are also
listed.
Defining the hydrate models

To ensure that reliable results are obtained it is particularly important that the
correct set of models and phase descriptors is used. The Hydrate model sets
contain a complete set of model and phase specifications (as do the relevant
hydrate model configuration files).
To define a hydrate model interactively, select Model Set from Select option in
the menu bar and click the Hydrates tab to activate the hydrates dialog box. The
Hydrate model is then defined by selecting the relevant hydrate phases, i.e.
Hydrate 1, Hydrate 2 or Hydrate H; the default is for hydrate1 and hydrate2 to be
selected. The thermodynamic hydrate model will calculate the hydrate
dissociation temperature or pressure, i.e. the point at which hydrates can form.
To predict the temperature or pressure at which hydrates will definitely form you
need to calculate hydrate nucleation. To do this you should also select Phase
Nucleation. Phase Nucleation in the list of phase descriptors always works in
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 189
conjunction with one of the solid phases such as any hydrate phase or the ice
phase. Therefore the selection of Phase Nucleation does not increase the number
of phases associated with the model used.
The hydrate model sets and the hydrate model configuration files have the
following definitions.
Fluid phase model

To carry out the full range of hydrate calculations with all the available
inhibitors the recommended fluid phase model is the advanced RKS equation of
state with the a parameter fitted to the pure component vapour pressure, the
Peneloux density correction and the Infochem mixing rule. The required binary
interaction parameters for hydrocarbons, light gases, water and inhibitors are
available from the OILANDGAS BIP dataset. However, for inhibition with
methanol or MEG CPA may be preferable as it reproduces the partitioning of
methanol, and MEG between water and hydrocarbon vapour and liquid phases
more accurately than RKSA plus NRTL style mixing rule. As a result it will
usually predict less conservative results for the amount of methanol required for
a fixed inhibition. The differences between the model predictions will be most
marked for systems with low water content and/or significant amounts of C6+.
Hydrate model
The thermodynamic hydrate model consists of lattice parameters for the empty
hydrate and parameters for the interaction of gas molecules with water in the
hydrate. There are different parameter values for each hydrate structure, Hydrate
1, 2 and H. In addition the hydrate must be associated with a liquid phase model
that is used to obtain the properties of water. It is important that this is the same
model that is used for water as a fluid phase.
Nucleation model
This model can be used to predict the nucleation of any hydrate phases and
provides an estimate of the temperature or pressure at which hydrates can be
realistically expected to form. The nucleation model is based on the statistical
theory of nucleation in multicomponent systems.
With the Infochem hydrate model described above and the nucleation model, the
hydrate formation and dissociation boundaries can be predicted. Between these
two boundaries is the area of hydrate risk.
Ice model
Ice is treated as a pure solid phase. The Infochem freeze-out model can be used
to model the solidification of any component. As with the hydrate phase it is
necessary to associate the solid phase model with a liquid phase model that is
used to obtain the properties of water. It is important that this is the same liquid
model that is associated with the hydrate phase. The nucleation model can also
be used to predict the temperature or pressure at which ice starts to nucleate.
Phases
In most cases six phase descriptors (PDs) are required: gas, hydrocarbon liquid,
aqueous liquid, hydrate 1, hydrate 2 and ice. At high pressures and/or low
temperatures the gas phase may become liquid-like and a second non-aqueous
liquid PD is needed. This is also the case if there is a significant amount of CO2
or H2S present. When considering structure H hydrates an additional phase
descriptor is needed for hydrate H.
190 Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
In most practical cases a natural gas contains propane and the stable hydrate
structure will be hydrate 2, although for very lean gases at higher pressures
hydrate 2 may be the most stable form. Key components are defined to
distinguish between the hydrocarbon and aqueous liquid phases.
The phase names used in the hydrate models are: GAS, LIQUID1, LIQUID2,
Water, Ice, HYDRATE1, HYDRATE2 and HYDRATEH. You can apply Phase
Nucleation to any of the solid phases (hydrates or ice) defined by the hydrate
model. If Phase Nucleation is selected, this means that the nucleation model is
defined and can be used to predict the nucleation of any of the hydrate phases or
ice.
In contrast to the thermodynamic hydrate model which allows all possible phases
to be present when carrying out calculations, the nucleation model considers
only the nucleation of the specified phase. At low pressures this can lead to
predictions that the hydrate formation temperature is higher than the dissociation
temperature. However, this is not a real situation as ice is not being allowed to
form.
Hydrate calculations with Multiflash

In principle, hydrate calculations with Multiflash are no different from flash
calculations for fluid phases alone. Multiflash treats fluid and solid phases on the
same basis and the full range of flashes can be carried out for streams with
hydrates.
An important point to note is that you must include water in the mixture
explicitly if you wish to do hydrate calculations. Unlike some other programs
Multiflash does not assume that water is present unless you specify it. The
amount of water may influence the results of the calculations, particularly when
inhibitors or water-soluble gases are present.
It may be useful for this case study to look at the results alongside the phase
diagram for the system, shown below
Phase Diagram for Methane/Butane/Water
1000
LH critical point
100
hydrocarbon VLW
phase envelope
hydrate line
Press/bar
10 water dew point

VLH
VLI
VW V
1
VI
ice line
0.1
150 200 250 300 350 400 450 500 550
Temp/K
Will hydrates form at given P and T ?
To find out whether a mixture will start to form hydrates at a given pressure and
temperature it is simply necessary to define your mixture, specify a hydrate
model set and do a P, T flash. If you wish to start from a problem setup file we
have provided hyd1.mfl
To define the case study interactively:
Select Select, then select Model Set, followed by selecting Hydrates tab to
activate the Hydrates dialog box. In the dialog box, select the relevant phases
required and initially specify RKSA (Infochem) as the fluid phase model.
Click on OK once the hydrate model set has been successfully defined and
loaded.
Specifying the components and composition
We will use a simple binary mixture plus water for this case study, but in
practice it is common to calculate hydrate dissociation and inhibition with large
multicomponent streams including several petroleum fractions. The mixture
chosen consists of 0.5 mol methane, 0.5 mol butane plus water.
Define the components in the usual way; click on the Select components
button, enter the component name in the Enter name text box and press the
enter key or click on Add to select them for loading into Multiflash. Click on
Close
Click on composition and enter the correct number of moles for each
component. Add 1.0 mol of water.
Enter the temperature, 250K and the pressure, 10 bar (remember to change the
standard pressure units from Pa to bar)
Click on the P,T flash button
You will see the following results in the results window.
Hydrate 2 is formed at the specified conditions, and you can see that this is in
agreement with the phase diagram. Note that the output shows the amount of
hydrate formed just as it does for other phases.
Hydrate formation and dissociation temperature

at given pressure
The hydrate formation or dissociation temperature calculation is an example of a
fixed phase fraction flash. The dissociation temperature is the point below which
hydrates can form (also known as the equilibrium hydrate formation curve). The
formation temperature is the point at which the nucleation of hydrate occurs and
P
H y d r a te z o n e H y d ra te H y d rate free
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s
s
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r H y d r a te f o r m a ti o n c u r v e H y d r a te d i s s o c i a ti o n c u r v e
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T e m p e r a t u r e
hydrate will form. Between these two points is the area of hydrate risk where
hydrates may or may not form depending on the time scale.
To calculate the hydrate dissociation temperature at given pressure
Retain the pressure at 10 bar
Click on the Fixed Phase Fraction Flash at specified pressure button,

In the dialogue box which is then activated, click on the button next to Select
phase and from the list select Hydrate2. Select Normal from the Type of
solution and enter 0.0 for the molar phase fraction
Click on Do flash
The results,
show that the hydrate first begins to form at 273.236K. It is important to specify
the correct hydrate structure to search for. If Hydrate1 was specified in the
above example the calculation would fail because there is no solution where
hydrate1 is more stable than hydrate2. In most cases of practical interest
hydrate2 is the structure formed, although hydrate1 may be more stable at high
pressures for streams containing a high concentration of methane or H2S. If
hydrate1 is more stable and if there are enough components present in the
mixture, hydrate1 should be present in non-zero amount in the list of phases
formed. If in doubt you can check with the P,T flash option which reports which
structure is stable.
Hydrate formation temperature at given pressure

To calculate the hydrate formation temperature at 10 bar, make sure the
nucleation model has been defined. Then select Nucleation from Select basis
in the Fixed Phase Fraction Flash at specified P dialog box., Set the phase
fraction text box to zero as before and then click Do flash button.
The calculated results with the nucleation model are displayed in the main
screen. Note that the hydrate formation temperature at 10 bar is now 263.42K,
about 10 Kelvin lower than the hydrate dissociation temperature, 273.2K.
If you try to calculate the hydrate formation temperature without first defining
the nucleation model, then the calculation will not converge and error messages
will occur in the screen:
Fixed phase fraction flash (nucleation):

Pfracflash;
*** ERROR 20292 ***
*** ERROR 20024 ***
may be no solution.
*** ERROR 344 ***
If this happens, define the nucleation model by selecting Phase Nucleation in the
Hydrates model dialog box and repeat the calculation.
Hydrate formation and dissociation pressure at

given temperature
The hydrate formation or dissociation pressure calculation is analogous to the
formation or dissociation temperature calculation, but is carried out with the
fixed phase fraction flash at specified T option (using the appropriate button or
menu option). The following example finds the hydrate dissociation pressure for
the above mixture at 250K.
The hydrate first forms at 3.6 bar. Under these conditions the hydrate forms from
the ice phase rather than the liquid water phase. The hydrate formation pressure
at the same temperature is 0.783 bar.
Hydrate phase boundary
You can also use the phase envelope calculator to plot the hydrate phase
boundaries for formation and dissociation for this stream by using the
thermodynamic hydrate model and nucleation model.
You will notice that at low pressures hydrate formation apparently occurs at
higher temperatures than hydrate dissociation. You are referred to Phases on
page 205 for a discussion on the reasons for this.
Other flash calculations with hydrates

Once the hydrate model has been specified it is possible to do the same flash
calculations as for other fluid phases. For example, an isenthalpic flash
calculation can be carried out in the same way as shown for the oil and gas
system, see Other flash calculations on page 188.
Maximum water content allowable before

hydrate dissociation
Multiflash can determine the maximum amount of water that may be present in a
mixture at a given pressure and temperature before hydrates can form.
This is an example of a Multiflash tolerance calculation. The overall
compositions must be specified on a water-free basis. A second mixture
composition is then specified using the Composition of Second Fluid tab in
the Tolerance Calculation dialogue box.
For a water tolerance calculation this would be pure water. The fixedphase
and phase fraction can be specified using the Select phase and Enter phase
fraction boxes, zero molar phase fraction of hydrate2 in this case. The
tolerance calculation combines the two mixtures in different ratios
until the specified condition is met. The following example finds the maximum
water content for the above mixture at 250K and 10bar.
As the overall composition must be specified on a water free basis, first remove
water from the mixture by:
Clicking on Composition and entering 0.0 for the amount of water. Water
must remain in the components list.
Select Calculate from the menu bar, then select Tolerance Calculation.
Select the required phase from Select phase box by clicking the downward-
arrow on the right side of the box, then set phase fraction to zero in Enter phase
fraction box.
Click the Composition of Second Fluid tab to obtain the second stream of the
mixture, then set the composition of water to 1.0 mole and leave the rest to zero.
Click Calculate to carry out the tolerance calculation. Click Close back to the
main window.
In the results window you will see
The first column shows the overall composition at the hydrate dissociation point.
The predicted maximum water content is 38.3 PPM on a molar basis. The
amount of second fluid added is the number of moles of water specified by the
tolerance calculation which must be mixed with the original water-free stream to
meet the condition of zero hydrate phase.
Calculations with inhibitors

There is no fundamental difference between calculations with and without
inhibitors. To investigate the effect of an inhibitor you can either add it to the
list of components in the mixture and specify the amount in the total mixture just
as for any other component or you can use the Inhibitor Calculator (see
Inhibitor calculator on page 101) to add the amount of inhibitor relative to
water. However, the inhibitor will not, of course, remain solely in the water
phase but will partition between the different phases present at equilibrium and
the amount in a particular phase will depend on the conditions and the amounts
of other components. This is exactly what happens in reality.
All the calculations described above can be carried out in the presence of
inhibitors.
Can hydrates form at given P and T ?

This is based on a P,T flash calculation. The following example illustrates the
calculation for an equimolar methane/butane mixture with water plus 35% by
mass of methanol relative to the water. Using Tools/Inhibitor Calculator bring
up the Inhibitor calculator window and add 35 mass% methanol to the 1 mole of
water in the system.
Alternatively 35 wt% methanol is approximately equivalent to adding 0.3 moles

to 1 mole of water. If you still have methane, butane and water loaded from the
previous example then add methanol using the Select Components option as
before. In the Composition drop down table enter 1.0 mol of water and 0.3
mol of methanol.
With the temperature at 250K and a pressure of 10 bar
Click on the P,T flash button.
The results show that even with the addition of inhibitor hydrates can still form.
However, there is now an additional free water phase which contains most of the
methanol.
Hydrate dissociation temperature at a given

pressure
With the same mixture, calculate the hydrate dissociation temperature using the
fixedphase fraction flash at fixed P with the hydrate 2 phase at 0.0 phase
fraction.
You can see that, compared to the earlier calculation in the absence of methanol,
the addition of methanol has reduced the hydrate dissociation temperature from
273K to 252K. Virtually all the methanol is in the aqueous phase at these
conditions.
Hydrate dissociation pressure at a given

temperature
Again this is analogous to the calculation above but you specify a fixedphase
fraction flash at fixed T. The hydrate dissociation pressure increases from 3.6
bar to 7.73 bar. The anti-freeze effect of methanol means that the hydrate forms
from liquid water rather than ice as previously.
Hydrate phase boundary

You can compare the hydrate phase boundary with and without inhibitor by
plotting the new phase boundary with methanol present.
Amount of inhibitor required to suppress
hydrates
Multiflash can determine the amount of inhibitor that must be added to the
system at a given pressure and temperature in order to suppress hydrates. This
is another example of a tolerance calculation and is therefore
specified using the Tolerance Calculation from the Calculate menu.
The overall compositions must be specified on an inhibitor-free basis. The
inhibitor is entered as a second stream using the tolerance calculation. The
phase required to be fixed and phase fraction can be specified in the Select
phase and Enter phase fraction boxes, zero phase fraction of hydrate2 in this
case. The tolerance calculation combines the two mixtures in different ratios
until the specified condition is met. The following example finds the amount of
methanol that must be added to suppress hydrates for the above mixture at 250K
and 10bar.
Remove methanol from the main stream by clicking on Composition and
entering 0.0 mol for methanol.
Select Calculate, then Tolerance Calculation to activate the Tolerance
Calculation dialogue box.
Select the required phase from Select phase box.
Set phase fraction to zero.
Click the Composition of Second Fluid tab to specify the composition of
methanol as 1.0 mole and leave the remainder zero.
Click Calculate to carry out the tolerance calculation.
Click Close to go back to the main window.
The first column shows the overall composition at the hydrate dissociation point.
The predicted methanol concentration required is 14.35% on a molar basis with
respect to the total stream, approximately 24.9 mol % with respect to water. The
amount of second fluid added is the number of moles of the mixture specified by
the tolerance calculation which must be mixed with the original inhibitor-free
stream to meet the condition of zero hydrate phase.
If the methanol concentration is required on a mass basis it is simple to change
the output units and recalculate the results.
Salt inhibition
Multiflash models for hydrate inhibition include the inhibiting effect of saline
water. The original salt model represents the salts as a single salt
pseudocomponent which can be loaded from INFODATA. As sodium chloride
is usually the dominant component, the model reduces other salt components to a
sodium chloride equivalent basis and the databank stores the molecular weight of
sodium chloride. The Electrolyte salt model introduced treats the salt as an
electrolyte composed of Na+ and Cl- ions. Future extensions will include
additional ions.
Unfortunately the information supplied for the amount of salt in brine, formation
or production water is not usually specified in the input format required. To help
you with the conversion we have provided a Salinity Calculator, see Salt
calculator on page 103 that converts various analyses into either the equivalent
amount of salt component or sodium and chloride ions.
To repeat the calculation for the hydrate dissociation temperature at fixed
pressure using salt, rather than methanol, inhibition:
Initially, select the RKSA(Infochem) model and 0.5 moles of methane, 0.5 moles
of butane and 1.0 moles of water as before.
Set the pressure units to bar and enter 10 bar for the pressure
Select the Inhibitor Calculator from the Tools menu and the tab for the Salt
Component Model
Enter 15 mass% NaCl in the Salt Analysis table
The Salinity Calculator will then determine that this is equivalent to adding
0.0544 mole of salt component to the 1 mole of water in the mixture.
and the salt component and this amount will be entered in the Composition drop
down table.
Specify the fixed phase flash at constant pressure, setting hydrate2 to 0.0, and
click on Do flash
The output shows that the hydrate dissociation temperature at 10 bar for this
stream is reduced from 273K to 265K.
To compare this to the results using the new salt model, return to Select
ModelSet and this time define RKSA(Infochem) + Electrolyte as the model.
Defining this model will automatically remove Salt component from the list of
components. With no salt present the hydrate dissociation temperature at 10 bar
is 273.2K, exactly the same as with RKSA(Infochem). Now from the Inhibitor
Calculator select the Electrolyte Model tab and enter 15 mass% NaCl in the Salt
Analysis table. This time .0544 moles of Na+ and .0544 moles Cl- are added to
the component list. The new salt model also predicts that the hydrate
dissociation temperature at 10 bar is reduced to 265.1K. Larger differences may
occur at higher salt concentrations.
CPA model
You can repeat the above calculations using the CPA model for the fluid phase.
The chosen mixture is not one where we might expect to see significant
differences between model predictions.
The predictions of hydrate dissociation temperatures and pressures are virtually
identical. The hydrate dissociation temperature at 10 bar with RKSAINFO was
273.236K, with CPA it is 273.238K. Similarly the hydrate dissociation pressure
at 250K was 3.6092 bar with RKSAINFO and is 3.6106 bar using CPA.
The partitioning results have been improved with the CPA model and the results
are seen in the tolerance calculations. The amount of water required before
hydrates form at 250K and 10 bar changes from 3.83e-5 mol (RKSAINFO) to
4.41e-5 (CPA) and the amount of methanol required to inhibit hydrate formation
at these conditions with 1 mole water present reduces from .3352 mole
(RKSAINFO) to .3223 mole (CPA).
CPA can only be used with the new electrolyte salt model. With 15 mass%
NaCl the hydrate dissociation temperature at 10 bar is reduced to 265.1K.
Case studies Wax deposition
Introduction
This section is only applicable if your copy of Multiflash includes the Wax
option.
Waxes are far more difficult to understand than pure solids because they are
complex mixtures of solid hydrocarbons that freeze out of crude oils if the
temperature is low enough. Waxes are mainly formed from normal paraffins but
isoparaffins and naphthenes are also present. As with hydrates the formation of
waxes is a serious concern in oil and gas processing.
Before discussing the modelling of wax deposition it is worth referring to a
paper by Erickson et al. SPE 26604, (1983). which compares the results of
measuring wax appearance temperatures (WAT) using three different
experimental techniques. For twelve oils, where there were measurements made
by at least two different techniques, there was only one case of complete
agreement between two methods. Otherwise the minimum difference between
techniques was 8 F, the maximum difference was 55 F, whilst the average
difference was 24 F. It appears that the accuracy of WAT measurements has
improved in recent years, but it is still difficult to measure; it is realistic when
assessing results to assume that experimental error in WAT values may amount
to several degrees.
Defining the wax model

There are two wax models in Multiflash. The wax model in earlier versions is a
multisolid model, whereas the new Coutinho model is a solid solution model.
Both are described in more detail in Modelling wax deposition on page 60.
Multisolid model
This model is associated with a model for the liquid phase, typically a cubic
equation of state. Originally we offered two fluid models from our standard
model set, RKSA and PRA but recommended the RKSA model. RKSA is now
the only fluid model accessible from the standard Model set window but the
PRA based version can still be used based on loading the waxpra.mfc file..
With the multisolid model the prediction of wax appearance temperatures is
particularly sensitive to the characterisation of the fluid; the carbon number
distribution and the properties assigned to each pseudo-component. As the PVT
Analysis facility is common to several models we have not defined the
characterisation procedure as part of the wax model, but allowed users full
flexibility. You should be aware though that your choice of where to start the
User Guide for Multiflash for Windows Case studies Wax deposition 205
pseudocomponents and the number of pseudocomponents your plus fraction is
split into can significantly affect the WAT predictions.
Our recommended procedure for the multisolid model is to start the
pseudocomponents from C6 and to split the plus fraction into 15 pseudo-
components, regardless of the experimental analysis of the distribution.
We have made every effort to include constraints and corrections that stabilise
the predictions. In general it appears from our tests that you should not split the
plusfraction into less than 5 or more than 15 pseudocomponents. Starting the
split from >C6 will usually tend to increase the predicted WAT but this will not
always be the case. Similarly, using the PRA model in place of RKSA usually
increases the WAT prediction by 3-4K.
Whatever the characterisation procedure chosen, if you have an experimental
value for the WAT you can use the matching procedure to amend the properties
of your pseudocomponents to reproduce the measured value.
Coutinho wax model

The Coutinho wax model is a solid solution model which requires more
information than the multisolid model. Predictions from Coutihno's model are
largely governed by the n-paraffin distribution. If no experimental data are
available for this it can be estimated from the total wax content. If this data too
is lacking then Multiflash has procedures to estimate this.
The n-paraffin distribution may be defined differently from that for the
remaining liquid phase but we have found that starting the n-paraffin
pseudocomponents from C6 and splitting the plus fraction into 15 pseudo-
components is again a useful default.
With a limited data set it is not possible to make any definitive statements
concerning the accuracy of the two models in predicting WAT, although it
would appear that Coutinho's model will predict a WAT slightly higher than the
multisolid model. What is clear is that Coutinho's model provides a much
improved prediction of wax precipitation as a function of temperature.
Calculating wax appearance temperature (WAT)

The calculation of the wax appearance temperature (WAT), formerly known as
the cloud point, is an example of a fixed phase fraction flash. To define the wax
model, select the Waxes tab in the Select/Model set option. Two wax models
are available in Multiflash..
206 Case studies Wax deposition User Guide for Multiflash for Windows
Select one of the models and click Define Model button to define the wax
model in the problem definition. Then Click on Close.
Go to the PVT Analysis form to characterise your fluid. The use of this is
described in detail in PVT Analysis on page 190. For the Multisolid model,
choose the Original Infonal1 method and complete the liquid composition table.
Set the Start pseudocomponents to C6 and number of pseudocomponents to 15.
Then Click on Do characterisation to characterise your fluid.
If you have selected the Coutinho model then you must choose the Revised
method (Infoanal2) for the distribution. If data are available you should provide
both the n-paraffin and other liquid hydrocarbon compositions and list these on
the "Single fluid with n-paraffins tab". You must then choose the split for both
liquid and n-paraffin distributions before completing your characterisation. If no
n-paraffin distribution is available then the liquid composition should be entered
on the Single Fluid tab and either the Total wax content enetered in the
appropriate text box or the box to estimate the wax content should be ticked.
This will activate the n-paraffin distribution and both this and the liquid
distribution should be defined before characterisation.
If you try to use a n-paraffin distribution with the Multisolid model then an error
message will be generated.
Fixed Phase Fraction Flash - at specified P (Mole
Fraction):
*** ERROR 15406 ***
The petroleum fractions are not suitable for the
Multisolid wax model.
*** ERROR 10022 ***
Model cannot be initialised
The WAT at any pressure can then be calculated by setting the pressure and
using the fixed phase fraction flash (at specified P) with Wax as the selected
phase with zero mole fraction.
or the phase envelope can be used to plot the wax booundary.
Our particular example is based on a supplied problem set up file called wax.mfl.
This particular fluid has a reported WAT of 45 DegC at 1 bar. The initial
problem is set up to use the Multisolid model.
The predicted WAT at one bar is 45.6 DegC.
Now return to the model selection and this time specify the Coutinho model. In
the PVT Analysis form select the Revised analysis method (nfoanal2). Tick the
estimate wax content box and set the n-paraffin distribution to start from C6 with
15 pseudocomponents and complete the characterisation. As you are using
Infoanal2 you will also see a plot comparing the experimental andfitted SCN
distribution.
The WAT at I bar is now predicted to be 49.4 DegC. Return to the PVT analysis
and, instead of estimating the wax content, enter 8.1% as the Total wax content
and complete the characterisation. This reduces the WAT to 48 DegC.
You may wish to vary the pseudocomponent split for the Multisolid model and
the n-paraffin distribution for the Coutinho model and see the effect on the
predicted WAT.
The wax phase boundary for both models can be generated and compared using
the phase envelope plotter.
If you have a measured values for the WAT then you can tune the
pseudocomponent properties for either model to match these values. This is done
using the Tools/Matching/Other phases option. The Matching option is
described in Matching using petroleum fraction properties on page 121.
For this particular example we know the WAT at 1 bar is 45DegC.
The matching facility will amend the values for the melting temperature and the
change of enthalpy on melting for all the pseudocomponents until the
experimental WAT is reproduced. The amended fraction properties are echoed
in the main window. For the Coutinho model it is the properties of the n-paraffin
fractions that are modified.
In this case we only have a sinle experimental WAT. The resultant wax phase
boundaries now show agreement at the matched WAT at 1 bar, but still exhibit
entirely different behaviour with pressure.
The wax boundary for a live oil has a different shape.
The full range of flashes is available for the Wax models.
Calculating wax precipitation

As with any other phase the amount and composition of the wax phase is
determined as part of any flash calculation. Using the Windows version of
Multiflash you can carry out a series of PT flashes to see how the wax builds up
as the heavier components solidify with decreasing temperature. However, if
you have the Excel add-in, this is an excellent way to see what is happening.
Precipitation of wax as a function of temperature

10.0
9.0
Coutinho model
Amounts of wax in fluid ( wt%)
8.0
Multisolid model
7.0 exp.
6.0
5.0
4.0
3.0
2.0
1.0
0.0
235 245 255 265 275 285 295 305 315
Temperature / K
We have supplied two spreadsheets, wax.xls and wax_new.xls, showing the

calculations in detail for the Multisolid and Coutinho models.
Case studies Asphaltene
flocculation
Introduction
One of the major problems for the oil industry is the precipitation of heavy
organics during production, transportation and the refining or processing of
crude oil. Asphaltenes are polar compounds that are stabilised in crude oil by
the presence of resins. If the oil is diluted by light hydrocarbons, the
concentration of resins goes down and a point may be reached where the
asphaltene is no longer stabilised and it flocculates to form a solid deposit.
Because the stabilising action of the resins works through the mechanism of
polar interactions, their effect becomes weaker as the temperature rises, i.e.
flocculation may occur as the temperature increases. However, as the
temperature increases further the asphaltene re-dissolves in the oil. Thus,
depending on the temperature and the composition of the oil, it is possible to find
cases where flocculation both increases and decreases with increasing
temperature.
The Infochem model for asphaltenes is based on a cubic equation of state but has
an additional term to describe the association of asphaltene molecules and their
solvation by resins. The parameters for the model have been developed from a
study of nearly thirty sets of experimental measurements of asphaltene
deposition which includes both proprietary and public domain data. The model
is complex and to ensure reliable results we recommend that you follow the
procedure we suggest until you are familiar with the model and the behaviour of
your particular fluid.
The asphaltene model in Multiflash is primarily intended for calculating
asphaltene flocculation from live oils. We are aware that many users have only
titration data for dead (STO) oils. We have investigated using this titration data
to set the asphaltene model parameters and this is discussed later in the case
study.
Input data
The ideal input data for the model are:
A compositional analysis of the live oil
The amount of asphaltene in the oil and the ratio of resin to
asphaltene, often determined from the SARA analysis
One set of flocculation conditions for the asphaltene flocculation
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 211
Bubble point (optional) to tune the petroleum fraction properties.
If a full SARA analysis is used to specify the weight % of asphaltene it is
important that it relates directly to the compositional analysis of the live oil.
Often the SARA will have been measured for the stock tank oil rather than the
total reservoir fluid. If you have the detailed compositions for separator gas and
liquid and the gas oil ratio (GOR) you should enter this data in the PVT Analysis
form for characterisation. In this case you can use the SARA as reported. If you
only have the reservoir fluid composition and the SARA from the stock tank oil
the weight % of asphaltene may be slightly in error. A quick way to correct the
weight % of asphaltene is to flash the reservoir fluid to stock tank oil conditions
and work out the mass percent of gas. In the SARA analysis add this to the
Saturates (S) text box and re-normalise the SARA when this option is offered.
For some samples you may only know the absolute weight % of asphaltenes and
resins in the total live oil but not the full SARA analysis. In these cases you can
just use the weight % of resins and asphaltenes and ignore the text boxes for
saturates and aromatics in the PVT Lab Fluid Analysis dialog box. For the
asphaltene model, the saturates and aromatics part of SARA are only used to
normalise the weight % of resins and asphaltenes.
If you do not have the complete data set we recommend we have developed
correlations to assign the required parameters. The minimum set of data in this
case are:
A compositional analysis of the live oil
Reservoir temperature
Bubble point (optional), to tune the petroleum fraction
properties.
Obviously the more data available the better the model predictions.
The prediction of asphaltene flocculation is not as sensitive to the
characterisation of the fluid as the wax models. However, we suggest you
consider using a common characterisation procedure. We recommend that in the
PVT Analysis facility you start the pseudocomponent split at C6 and split the
fraction into 15 components, regardless of the original experimental distribution.
Finally, to model asphaltene flocculation successfully you need to adjust one
model parameter to match actual flocculation data. If you have such
experimental data available then you match to this. If you do not have any data
there are two options. We have modified the screening procedure suggested by
De Boer et al to adjust the parameter based on a knowledge of the reservoir
conditions or you can use STO titration data if this is available,
Defining the asphaltene model

The cubic equation of state, RKSA, is defined as part of the model, it is not
possible to choose a different fluid phase model. This flexibility may be added
at a later date.
To set up the asphaltene model you can either load the asphalt.mfc file or use the
Select/Model Set option.
Select the asphaltene tab, Click on Define Model to select the asphaltene model
and Click on Close to load the model.
212 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
The default phases for the asphaltene model are gas, liquid1 and asphaltene.
However, you can add a water phase if you wish. In Windows this can be done
very simply by ticking the water check box. In the asphalt.mfc file we have
commented out the lines defining the water phase and the key component for this
phase.
If you wish amend the .mfc file you must edit it to remove the # sign before the
relevant lines.
The next step is to characterise your fluid. Go to the PVT Analysis form,
described in detail in PVT Analysis on page 110. Initially, set the Analysis
method to the original Infoanal2 method. Enter the fluid analysis and set the
Start pseudocomponents to C6 and the number of pseudocomponents to 15.
Enter any data you have on the molecular weight and/or specific gravity.
The final step in the characterisation is to enter any data you have on the weight
of asphaltene in the oil and the ratio of resin to asphaltene. The example we are
going to look at is based on a supplied problem set up file, asphex.mfl. We have
assumed in this example that a full SARA analysis is available, but later in the
case study we will go back and look at the options if you dont have this much
data.
If you load asphex.mfl the PVT Analysis form will look like this
Once you are happy the data is correct Click on Do Characterisation. In this
case a message box will tell you the characterisation has been successfully
completed and a plot of the data and fitted diistribtion. You can then Click on
OK and on Close to go back to the main window.
If you have any warnings or errors associated with your own examples then the
relevant message box will appear. Those related to fluid characterisation in
general are described in PVT Analysis on page 110. Since the release of the
asphaltene model we have had feedback from several users. In our original
database of asphaltene measurements the resin/asphaltene ratio was always
greater than 2.5. However, some of our users have reported values below this,
possibly because the SARA analysis was based on a different experimental
techniques. Depending on the actual R/A entered you may find that model
parameters cannot be generated. We have added a warning message if R/A is
below 2.5
you can either ignore this warning message and see if model parameters can be
produced or you can delete the Resin amount from the SARA and tick the
Estimate RA box and the model will generate a default R/A ratio.
After characterisation the asphaltene component(s) are denoted by an A prefix,
e.g. AS39+, and the resin component(s) by an R prefix, e.g. R39+.
The next stage is to use the matching facility to tune the pseudocomponent
properties and fix the one adjustable model parameter. We recommend that if
you have bubble point data available you tune the petroleum fraction properties
to match this. Matching the bubble point has been incorporated into the
asphaltene matching form.
In practice we have found that you do not always have to match to bubble point
data to model the asphaltene data, although you almost always need such
matching for light oils. In this particular example bubble point data were not
provided but we have used an appropriate value for demonstration purposes.
However, we do recommend use of the matching procedure for the asphaltene
phase. Although we have supplied a default for the case where you have no
information to fix the adjustable model parameter we cannot recommend any of
the subsequent results. But we do recognise that you may want to use the
asphaltene model for screening purposes and we have developed a procedure to
adjust this parameter based on a knowledge of the reservoir conditions or STO
titration data.
For this example the assumed bubble point is 250K and 70 bar and the reservoir
conditions are 365K and 343 bar. Use the Tools\Matching\Asphaltene Phase to
display the dialogue box, and enter the appropriate values.
Click on Match and Close: the model parameter values and the amended
petroleum fraction properties will be displayed in the main window. The
asphaltene model has now been defined.
Calculating asphaltene flocculation conditions

Once the asphaltene model has been defined and the parameters fitted you can
carry out flocculation calculations.
If you are starting from the position where you only know the reservoir
conditions and have no information on specific flocculation conditions we
suggest you should use the phase boundary tracer to get an overall picture. This
is extremely useful, but for these complex calculations it can be difficult to find
convergence or even starting values. We recommend you follow this procedure.
First plot the bubble point line. Use the Phase Envelope facility and plot the
boundary for zero gas phase, in this case with the initial values for pressure set to
75 bar.
Click on Plot to display the phase boundary. This will usually show two points
of discontinuity, labelled D. These are the points where the asphaltene
deposition envelope crosses the bubble point line.
These points can be very useful for setting an appropriate starting pressure for
the deposition envelope or providing starting values if these are required. For
this example go back to the Phase Envelope and this time set the phase to
asphaltene, the fraction to zero, the solution type to unspecified and the Initial
value for pressure to 170 bar. Ask for more points to be plotted until the
asphaltene boundary is complete.
For other examples you may have to plot the upper and lower boundaries
separately. The upper boundary uses the Unspecified solution or Upper
retrograde type solution, the lower boundary the Lower retrograde type of
solution. Alternatively you can try specifying temperature rather than pressure
and/or providing a starting value. We have found asphaltene boundaries most
difficult to plot for very light oils.
If you have a known set of conditions and want to see if, and how much,
asphaltene is present you can use a simple P,T flash. Enter the temperature and
pressure, for example 365K and 170 bar, Click on the P,T icon, or Select the P,T
flash from the Calculate\Standard flash menu. The phases present, and the
composition and amount of each phase, will be reported. Before doing this you
may find it useful to set the units for amounts to mass as this usually reflects the
units of measurement.
If you want to know the pressure at which asphaltene will start to deposit at any
given temperature then you should use a flash at fixed phase fraction and
temperature. Set the temperature, in this case 350K. Again Click on the icon or
select the calculation option and the dialogue box will appear.
Set the molar phase fraction to zero. To calculate the pressure at which
asphaltene will first appear for pressures above the bubble point, select
Unspecified or Upper retrograde as the solution type and Click on Do Flash.
Multiflash will calculate the pressure on the upper asphaltene phase boundary, in
this case 227 bar. To obtain the pressure for the lower asphaltene phase
boundary, below the bubble point, follow the same procedure but set the Type of
solution to Lower retrograde. In this case the reported pressure is 104.7 bar.
You can determine the amount of asphaltene flocculation at any set of P,T
conditions using an isothermal flash as described earlier, You may like to get
an idea of the amount of flocculation along any isotherm by carrying out a series
of 4 or 5 calculations.
Set a temperature, e.g. 350K and set the output units to mass fractions. Carry out
a P,T flash at a pressure above and below the deposition envelope. At 275 bar
and 100 bar the asphaltene will be fully dissolved in the oil with a mass fraction
of .012. This is equivalent to the SARA analysis of an asphaltene content of 1.2
mass %. Calculate the pressure for the upper and lower phase boundaries as
before, 228 and 104 bar, at this point the asphaltene is still fully dissolved.
Finally, carry out a bubble point calculation specifying a temperature of 350K
The amount of asphaltene dissolved in the oil is equivalent to 1.02 mass % and
this is the point of maximum deposition. Note the pressure, 132.8 bar. These
points can be plotted as shown below to give either the amount of asphaltene
dissolved in the oil or converted to show the amount deposited.
Asphaltene deposition isotherm 350K
1.25
1.2
Wt % asphaltene in oil
1.15
1.1
1.05
1
100 120 140 160 180 200 220 240 260
Pressure bar
Sensitivity of calculations to variation in input data
Choice of Analysis method

There is a choice of analysis method to characterise the fluid, the original
method, Infoanal1 and the revised method, Infoanal2, which can also be used
with and without a n-paraffin distribution. The intial calculations were carried
out based on the default Infoanal2 analysis method and matching to reservoir
conditions. The plots below show the effect of including the n-paraffin
distribution and changing to Infoanal1.
The resultant ADE are very close. Inclusion of a n-paraffin distribution will alter
the C6+ molecular weight used to derive one of the model parameters and for
this example this leads to a small reduction in the size of the ADE.
Data Availability
This example of asphaltene flocculation was based on a data set which
comprised the compositional fluid analysis, a SARA analysis, an assumed
bubble point and the reservoir conditions. In this case, as the bubble point was
assumed, the lack of bubble point data has no significant effect on the results.
However, there are other data that may be missing. In all cases the revised
analysis was used to characterise the fluid.
No information on the amount of asphaltene in the oil

We have provided a procedure to estimate the weight % of asphaltene in the oil
if this data is not available. In this case in the PVT Analysis box you should tick
the box for estimate RA, and then Click on Do Characterisation and Close.
Rematch the bubble point and asphaltene phase at the reservoir conditions as
before and plot the asphaltene deposition envelope (ADE). It is important to
include this step; the matching procedure is cancelled when the fluid is re-
characterised.
The default procedure estimates both the weight % of asphaltene and the
resin/asphaltene ratio. For this particular example the weight % of asphaltene
with Infoanal2 is very close to the reported value at 1.3 wt% asphaltene
compared to the experimental data of 1.2 wt%. With Infoanal1 the wt% of
asphaltene was underestimated at 0.44 wt% . This results in a difference with
Infoanal1 to both the ADE and the deposition isotherm.
No resin asphaltene ratio

Even if you do not have a SARA analysis you may have the weight % asphaltene
and only need to estimate the Resin/Asphaltene ratio. Proceed as before, enter
the wt% asphaltene (1.2 %) in the correct text box in the PVT Analysis but still
tick the Estimate RA box. Repeat the matching of bubble point and reservoir
conditions again and plot the ADE.
In this case the calculated the ADE are very close to that predicted with a full
SARA analysis whichever analysis method is chosen. This also applies to the
deposition isotherm at 350K.
No reservoir pressure
If you only have the reservoir temperature we have included a facility to estimate
this. Simply enter the bubble point and reservoir temperature as before and
initiate the matching procedure.
For this particular example the resultant ADE is almost indistinguishable from
the ADE calculated from the real reservoir conditions.
As a corollary to this we have noticed that you usually generate very
conservative ADE when you have a very over-pressured reservoir. If you have a
bubble point measurement at the same temperature as the reservoir temperature
and the reservoir pressure is more than 2.5 times the bubble point a warning
message is generated.
You can continue to match to your reservoir conditions although it may also be
beneficial to generate the model parameters with an estimated reservoir pressure
to see the likely sensitivity.
If, as in our case study, the bubble point is matched at a different temperature to
the reservoir temperature no warning is issued.
No reservoir or flocculation conditions

If you do not have either reservoir or flocculation conditions then there are two
default options for generating the asphaltene model parameters.
If you have entered a bubble point in the Asphaltene matching but nothing for
Reservoir conditions or Asphaltene formation then Multiflash will assume that
the reservoir temperature is the same as the bubble point temperature and
proceed to estimate the reservoir pressure as above.
If nothing is entered for bubble point, reservoir conditions or asphaltene
flocculation the model parameters are generated from correlations based on data
held in our database. The results from using this route are vary variable,
depending on the fluid analysis and we cannot recommend its use. In this case
the result would be a prediction that no asphaltene would flocculate. Extension
of our database may allow us to improve the default parameters.
Matching to asphaltene deposition data

The assumption in this case is that you have more data than our basic example,
real deposition data either from field conditions or a asphaltene flocculation
measurement. You simple repeat the procedure but at the Matching/Asphaltene
Phase step you replace the selection of Reservoir conditions with Deposition
envelope. We have assumed a value of 200 bar at 365K
which gives a much smaller ADE
and a different asphaltene isotherm.
Asphaltene deposition isotherm 350K
1.25
1.2
Wt % asphaltene in oil
1.15 Match to assumed deposition data
1.1
Match to reservoir conditions
1.05
1
100 120 140 160 180 200 220 240 260
Pressure bar
Gas injection
It is known that as gas is injected into a reservoir the likelihood of asphaltene
flocculation is increased. The asphaltene model predicts this trend correctly.
Return to the original ADE, calculated from the asphex.mfl input file with
matched bubble point and reservoir conditions. You can mimic gas injection by
increasing the amount of methane by adding more moles of methane in the drop
down composition box. If you increase the amount of methane from 27.55
moles to 40 moles and replot the ADE you will see that the fluid bubble point
line is at higher pressures and the ADE has expanded.
When looking at the effect of gas injection you should, of course, not rematch
the fluid bubble point or asphaltene phase deposition as doing this will alter the
petroleum fraction properties and model parameters.
You should not use the PVT Analysis GOR option to add the injection gas to the
reservoir fluid. Any re-characterisation cancels the properties and parameters
derived from earlier matching and, as you now have a different fluid, the values
of bubble point and reservoir conditions used for matching are no longer valid.
If you have a complex injection gas and want to study the effect of different gas
injection rates then we suggest the use of an Excel spreadsheet.
Titration
The Infochem asphaltene model was intended for use in predicting the
asphaltene flocculation of live oils and the model parameter generation based on
asphaltene studies of live fluids. However, live oil asphaltene studies can be
expensive, particulalry with the requirement to obtain and transport bootom hole
sales. Some of our users have asked whether titration measurements on dead oils
can be used to generate the model parameters. To date we have only been able
to obtain limited samples of titration data and have traced only one oil, in the
public domain, where there is any information on both asphaltenes in the live oil
and reported titration on the associated stock tank oil (STO), enabling us to
compare results. However, we understand that some of our users have applied
this approach successfully, and for Multiflash 3.3 we have automated the
procedure.
The studies have been limited to titration with heptane.
Our example is based on the titration.mfl file provided. The file includes the live
oil composition and the wt% asphaltene. The reported value was 1.9 wt% for
the STO, but has been corrected to 1.62 wt% for the live fluid using the method
describe earlier, see Input data on page 211.
Characterise the fluid composition as usual and the return to the main menu,
Tools/Matching/Asphaltene phase. The reported amount of heptane to just cause
asphaltenes to flocculate from the STO at ambient conditions is 1.4 cm3 per g
tank oil. This has been converted to .962 g heptane using the known density.
Enter this value and click on match.
The asphaltene model parameters will be reported in the main window as usual
and the ADE plotted. The resultant ADE is compared to those generated from
matching to a known flocculation point of 54.4 C and 200 bar and to a
combination of reservoir temperature (54.4 C and bubble point (54.4 C and
156.2 bar)
The ADE predicted from matching to titration of the STO is more conservative
than the ADE from flocculation measurements but less conservative than using
reservoir conditions to provide the model parameters. It is believed this has been
the experience for other fluids.
If your titration data does not include the amount of heptane just to initiate
flocculation and it is not possible to deduce this from the other titration results
then the procedure for parameter generation is slightly more complicated and
requires the use of an Excel spreadsheet. In Multiflash for Windows either
characterise the STO, if this composition is provided or flash the characterised
live oil to STO conditions. Using the STO composition match the asphaltene
flocculation to ambient conditions and make a note of the RAE parameter. Save
the problem using the File/Save Problem Setup option. You then need to create
an Excel worksheet to read in this .mfl file. Details of how to do this are
described in the Excel manual. For our example we have generated the file
STO_titration.mfl
You then need to do two things: add a new component to the list, heptane, and
add the command line describing the asphaltene parameters. This can be copied
from Multiflash for Windows using Tools/Show/Problem However it must be
set up so that the RAP parameter appears in a single cell so that it can be
optimised using the Excel Solver, e.g.
include c:\work directory\exampleoil.mfl";
model MREFASPHALTENE RAEQUIL DATA AAPREEXP
1.00000000 AAEXP 1.00000000 RAPREEXP
0.62542
RAEXP
0.98213 ;
component heptane;
The spreadsheet, titration.xls is then set up to calculate the wt% of asphaltene
deposited for the experimental amounts of heptane added which can then be
compared to the reported wt% asphaltene deposition. This is then used to
optimise the value of RAPREEXP (RAP) using the Excel Tools/Solver.
For our particular example the data reported in the paper included a live oil and a
STO composition, a wt% asphaltene for the STO, which we also corrected to
live oil composition, an asphaltene flocculation point and five points for the
heptane titration.
The reported titration data are plotted below
wt% asphaltene component precipitated as Fn C7 solvent
1.8
1.6
1.4
wt% asphaltene
1.2
0.8 Exptl
0.6
0.4
0.2
0
0 5 10 15 20 25 30 35 40
g C7/g oil
Fitting to the onset flocculation point using the matching facility produced the
following parameters
RAE 0.981265
RAP 0.71881
Whereas fitting to the other four points in Excel gave parameters
RAE 0.98213
RAP 0.68517
These parameters repreent the STO titration data well.
wt% asphaltene component precipitated as Fn C7 solvent
1.8
1.6
1.4
wt% asphaltene
1.2
1
RAP fit
0.8 Exptl
0.6 predicted onset
0.4
0.2
0
0 5 10 15 20 25 30 35 40
g C7/g oil
The ADE predicted using model parameters generated this way is more
conservative than the ADE generated using onset titration data, which is in turn
more conservative than that generated from flocculation data.
It is clearly preferrable to generate the live oil ADE from live oil data. Some
predictions are possible from titration data but is is important that all data are
compatible, particularly the compositions of the STO and the flashed liquid.
Case studies Combined solids
Introduction
The previous three case studies looked at solid formation for hydrates, waxes
and asphaltenes as separate problems. However, for some fluids at certain
conditions it is possible that any or all of these may form at the same time. The
formation of any one will affect the overall composition of the fluid and may
therefore affect the formation of the other solidsTo examine this possibility we
have included a Combined Solids model option. The particular model options
for each solid have been chosen to provide the best Infochem can offer whilst
ensuring compatibility. The common fluid phase model is RKSA. The hydrate
models therefore use RKSAINFO as the fluid model, combined with the
Electrolyte salt model. The wax model is Coutinho and there is only one
asphaltene model. The Combined Solids option is only designed to look at solid
formation, if you want to study the more complex problems such as hydrate
inhibition you should still choose the dedicated Hydrates model set. In fact, you
will see messages to this effect if you only choose a single solid phase in the
Combined Solids option.
Asphaltene flocculation
To understand what happens when more than one solid forms a useful starting
point is to examine asphaltene flocculation alone. The example input file
provided is combsolid.mfl. This includes an oil composition to C20+ which has
a molecular weight of 81, wt% resin of 12.04 and wt% asphaltene of 0.7. The
fluid is characterised from C6 with 15 fractions. The resins and asphaltenes are
allocated as shown below:
25R R67-75 .692746
26R R75+ .516726
27AS ASPHALTENE .700000
The asphaltene model parameters are matched with a bubble point of 120F and
2650 psia and an asphaltene flocculation point of 120F and 8750 psia. The
predicted ADE is plotted below.
User Guide for Multiflash for Windows Case studies Combined solids 229
Wax and Asphaltene precipitation
To see the effect of simultaneous wax and asphaltene precipitation we first need
to re-characterise the fluid with a n-paraffin distribution in order to apply the
Coutinho model. In the PVT form tick the bos to estimate wax content as none
is known. The n-paraffin distribution is also set to C6 and 15 fractions.
The separation of the n-paraffins from the remainder of the liquid also alters the
distribution and properties of the resins and asphaltenes:
19RI R33-37 1.90353
20RI R37-42 2.53946
21RI R42-47 2.26335
22RI R47-54 1.96595
23RI R54-63 1.66832
24RI R63-74 1.16583
25RI R74 1.682065E-02
26RI R75+ .516726
27AI ASPHALTENE .700000
This in itself will alter the resin/asphaltene interaction. Allowing the wax to
form will then remove some of the n-paraffins from the fluid again changing the
proportion of resins in the remaining fluid.
To see the effect choose the Combined Solids option from Select/Model set and
specify wax and asphaltenes as the solid phases. Eliminate Hydrates, water and
ice for the time being.
230 Case studies Combined solids User Guide for Multiflash for Windows
As the model has been re-defined we will need to match the asphaltene
parameters again, using the same input data. The new parameters will be
slightly different because of the altered distribution.
Now plot the gas and asphaltene boundaries as before then add the wax
boundary.
As you can see changing the resin distribution and removing some of the n-
paraffins has the effect of stabilising the asphaltene and thus lowering the upper
ADE once wax has formed.
Hydrates, Waxes and Asphaltenes

To study the effect of allowing hydrates to form we can retain the fluid
characterisation used for wax and asphaltene but need to add water. Do this
using Select/Components. Initially set the water composition to zero.
Return to the Combined Solids selection and add the hydrates, water and ice to
the list of potential phases.
As we have chosen to re-define the model we also need to re-match the
asphaltene parameters. This is best done in the absence of water, which is why
the initial water composition was set to zero. Using the same input data the
asphaltene parameters will be exactly the same as for the wax and asphaltene
study.
Now add the water composition, 10g. Adding too much water may cause
difficulties when plotting the ADE.
With water present use the phase envelope plotter to generate all the phase
boundaries. Starting point for the asphaltene bounday may have to be changed
as it is affected by the presence of the other solids.
The wax boundary is not affected by the addition of water or the formation of
hydrate, which occurs at lower temperatures. However, the effect on the upper
ADE is significant. As the hydrate is formed the light gas hydrate formers are
removed from the fluid. This is in effect the reverse of gas injection and the
asphaltene is stabilised with flocculation occuring at lower temperatures.
Of course with water present there is also the possiblity of a separate water phase
232 Case studies Combined solids User Guide for Multiflash for Windows
If the fluid is flashed at 70F and 1750 psia Multiflash will predict the formation
of 6 phases; gas, hydrocarbon liquid, water, hydrate, aspahltene and wax. With
only 10g of water present reducing the temperature slightly removes the water
phase owing to the formation of additional hydrate.
Of course, in practice the formation of some many phases will be affected by
kinetics as well as thermodynamics.
Case studies Excel
spreadsheets
Introduction
Although only accessible if you have licensed the Excel add-in option there are
some problems which are best approached using Excel. Some of these are
discussed in the Multiflash Excel manual, such as generating tables of pure
component data or using linked flashes or recycles for simple flowsheet
calculations.
Those presented here were set up following user requests and include generating
binary interaction parameters for activity coefficient models and linking
predictions of solid formation to a common fluid analysis.
Although we have not included them here some users wish to fit their own
experimental data for components not included in their version of Multiflash. To
help users to do this we do have available a series of spreadsheets for the fitting
of pure component data. They are not issued with the standard installation but
we will supply them on request.
UNFACFIT.xls
UNIFAC is a very useful model as the binary interaction parameters are
generated from the group structures of the pure components and so reasonable
predictions of phase equilibria can be obtained for polar systems without the
need for stored BIPs.
However, there may be times when you wish to use an alternative model such as
NRTL. Although we are continually expanding our BIP databank there may be
some binary pairs in your mixture for which we do not have stored NRTL
parameters. If you do not have the time to search for experimental data for the
missing pairs, or are unable to find any, then this spreadsheet allows you to
generate the phase equilibria data from UNIFAC, providing group structures are
available for your chosen components, and then fit this data using another
activity model.
The spreadsheet has several worksheets.
Notes
The first spreadsheet consists of notes on how to use UNFICAFIT.xls and how
to enter the fitted BIPs in Multiflash.
User Guide for Multiflash for Windows Case studies Excel spreadsheets 235
UNIFAC
This is the worksheet where you generate the phase equilibria data (liquid and
gas phase compositions and temperature or pressure) that you are going to fit.
You specify, by entering information in the appropriate cell:
The databank to act as the source of pure component data, either
Infodata or DIPPR
The names of the two components for your binary pair
Whether you wish to generate data for an isotherm or isobar and
your chosen temperature or pressure
The required data is then generated, including column headings and plots. The
composition range is fixed and the units are SI. There is no need to change these
although it is possible.
An Error box reports the status of the data generation. This should be OK if the
UNIFAC group structures are available for your chosen components. An error
status of 13201 would indicate that the structures are missing for one or both
compounds.
Once the data has been generated you can move to the worksheet for the model
you wish to use, WilsonE, UNIQUAC VLE or NRTL VLE.
Activity model worksheets

All the model worksheets function in a similar manner. The component names,
conditions, temperature or pressure are copied from the UNIFAC worksheet as
are the phase equilibria data. The user enters initial guesses for the BIPs, a
useful default is to start with 0.0 for both, and using the Excel Tools/Solver to
start the fitting procedure. Once the best solution has been reached the new BIPs
will be reflected in the cells used for starting guesses and in the cells reporting
the fitted BIPs. One of the useful benefits of using Excel is that the results are
plotted for comparison with the UNIFAC generated data allowing the user to
decide easily whether the solution is acceptable.
If the solution is not acceptable then you can try
starting with a different initial estimate for the BIPs
using a different criteria for minimisation. The default setting is to
minimise on the sum of squares of the differences between given
and predicted temperature or pressure. It is possible to minimise
on differences in gas composition by changing the target cell in the
Solver.
Change the constraints on the values for BIPs when fitting. We
have set limits on the values the BIPs can take as part of the
Tools/Solver utility. It is again possible to change this constraint
using the Change button on the Solver text box.
Once acceptable BIPs have been generated they can be entered and stored in
Multiflash as described in the spreadsheet notes or Supplementing or
overwriting BIPs on page 78.
Although NRTL has three parameters we have chosen not to fit all three but to
default the third parameter, alpha, to 0.3. You can over-ride this if you wish but
we would suggest that values for alpha should never be negative and should
rarely be larger than 0.6.
Currently the fitting is limited to constant values for the BIPs although this could
be expanded if necessary.
236 Case studies Excel spreadsheets User Guide for Multiflash for Windows
VLEFIT.xls
This is substantially the same as UNIFACFIT.xls but the starting point is
experimental data rather than data generated from the UNIFAC model.
Instead of the first UNIFAC worksheet there is an Experimental worksheet to
enter the data. Again you can choose the data source for your pure component
data and indicate whether your chosen data is along an isotherm or isobar. In
order to minimise effort this spreadsheet does allow you to choose the units for
temperature and pressure to match those measured. The temperature or pressure
for the isotherm or isobar should be entered as should the values for x, y and
associated T or P.
We have chosen a limited array for data entry. If you have more data and are
familiar with Excel you can extend the range although you will need to
remember to change the cell references in the dependent worksheets. Otherwise
you should limit the data by choosing suitable sets from the data available.
If you have less data then you should enter #N/A in the cells which would
otherwise be empty or retain values for earlier entries. This is necessary for the
Excel Solver to operate correctly. For some data sets you may have P,x or T,x
but no data for gas composition, y. In this case it is better to enter #N/A for the y
compositions. If you fail to do this the Solver will still function provided the
minimisation criteria is based on difference in temperature or pressure the
default. However, the plots for x,y will not be relevant and should be ignored.
As with UNIFACFIT.xls you can fit the experimental data to generate BIPs for
WilsonE, UNIQUAC VLE or NRTL VLE by choosing the appropriate
worksheet.
Solids.xls, Solids31.xls and Solids32.xls

Several of the engineers using Multiflash for Windows have found it fairly
complex to obtain results for solid formation particularly for asphaltenes.
Improvements to allow users to fit bubble point and asphaltene model
parameters at the same time go some way to alleviating this problem. However,
we had set up a spreadsheet, solids.xls, which many engineers find useful and
which we have decided to issue as part of the implementation. Of course you
will only be able to use any worksheet if you have licensed the appropriate
model.
This spreadsheet takes a common PVT fluid analysis and uses this as the input
composition to match and/or predict bubble point and hydrate, wax and
asphaltene formation.
Again the spreadsheet consists of several worksheets and each worksheet has the
relevant models built-in in hidden rows or columns. The default model for
hydrate formation and inhibition in solids.xls is based on RKSAINFO.as the
fluid model as, at the original date of issue, the CPA model could not deal with
salt. With the introduction of the new electrolyte salt model we have provided
an additional spreadsheet, solid31.xls. This includes the updated asphaltene
model and the hydrate calculations are based on CPA+Electrolyte. With the
issue of the Revised PVT characterisation method, a new spreadsheet,
solids32.xls is provided which includes the new PVT analysis, asphaltene and
CPA+Electrolyte models.
The Excel calculations are set to manual using the Excel Tools/Options facility.
This is to prevent automatic calculation of the whole spreadsheet as new
compositions are entered. To update any individual worksheet use Shift F9, to
update the whole spreadsheet use F9.
PVT Analysis
This work sheet characterises the fluid according to the fluid composition
provided. In common with our other spreadsheets input data are marked in red.
The list of possible components is based on the default component list used in
our PVT Analysis utility. The user enters the compositions and any other
information available such as the molecular weight and specific gravity. The
SARA analysis can be entered; the resin and asphaltene amounts are needed for
the asphaltene model although they can be estimated if required. The user can
specify the starting point and the number of fractions for the characterisation
although we would recommend staying with C6 and 15 fractions. The units for
calculation are also set in this worksheet.
Once the characterisation has been carried out a bubble point is predicted using
this characterisation at a temperature or pressure set by the user. This allows the
user to decide whether to tune the petroleum fraction properties to match a
known bubble point or if this is unnecessary.
Match bubble point

If the predicted bubble point is sufficiently different from a known value then
this worksheet allows the user to match a known bubble point. The fluid
composition is taken from the characterised fluid in the PVT Analysis
worksheet. The user specifies the bubble point to be matched and the bubble
point is recalculated after the match to confirm that this has been carried out. A
new problem input specification is written into this worksheet as a result of the
match but it is in hidden rows or column.
Wax
The next worksheet is dedicated to prediction of wax formation, although the
worksheets for wax, asphaltene and hydrates are not inter-dependent and can be
used in any order.
The user can choose to use the fluid characterisation direct from the PVT
Analysis or with petroleum fraction properties tuned to match a bubble point.
The first set of calculations predict the wax appearance temperature (WAT)
without any further tuning plus the amount of wax formed at a user specified
T,P. The WAT is plotted automatically as a function of pressure. The starting
pressure and step can set by the user to obtain the pressure range of choice.
These calculations are repeated based on matching to a known WAT.
Asphaltenes
The asphaltene worksheet again offers the choice of using the PVT Analysis
characterisation direct or the characterisation after matching to a known bubble
point. For asphaltene modelling we would recommend the latter.
The options for producing the asphaltene model parameters are not as flexible in
Excel as in the Windows front end. You are limited to two options, the
flocculation or reservoir conditions and you must supply both temperature and
pressure.
After matching the user can set either temperature or pressure and calculate the
corresponding P or T for the upper and lower boundaries of the flocculation
envelope. There is also an option for entering a set of T,P and calculating the
amount of asphaltene formed at those conditions.
Every effort has been made to plot the asphaltene flocculation envelope
automatically with starting points derived from the flocculation or reservoir
conditions. However, as the engineers using our Windows phase envelope
facility will appreciate it is difficult to make this absolutely foolproof.
Asphaltene with gas injection

The effect of gas injection on asphaltene flocculation is most easily calculated in
Excel. The asphaltene model parameters for any fluid should be retained when
studying the effect of added gas and the gas injection worksheet is therefore
dependent on the asphaltene worksheet for the problem input specification and
the matching function is disabled. It serves only to report the conditions chosen
for matching.
The composition of the gas is entered and the ratio of gas to oil is based on a
simple molar ratio.
You can still change conditions of temperature and/or pressure to determine the
boundaries for flocculation and the amount of asphaltene flocculated. The
boundaries for asphaltene flocculation, with and without gas injection are plotted
but it cannot be guaranteed that this will be available for all fluids and gas
injection rates.
Hydrates
The hydrate functionality is well served in our Windows software and easily
used. We have only added a hydrate worksheet here for completeness and to
allow the engineer to carry out quick checks for possible hydrate formation. It
encapsulates the main features of our hydrate model but does not have the
flexibility of the Windows program.
The model used in solids.xls is based on RKSA (Infochem) as the fluid phase
model, in solids31.xls the model is based on CPA and the new salt model.
The user needs to add an amount of water to the fluid and this can either be pure
water or produced water with the salt content defined by ion analysis or total
dissolved solid. The hydrate dissociation temperature can be calculated at a
single pressure or plotted as a function of pressure. The hydrate is defined as
hydrate2 only, which is the usual hydrate formed especially as the spreadsheet is
designed to work with oils rather than natural gases.
There is also a section in the worksheet for looking at the use of inhibitors.
These are limited to the two most common, methanol or MEG. They can be
added in fixed amount or the concentration required for hydrate inhibition at set
conditions can be predicted.
Users who want to investigate hydrate behaviour only may find the
hydrateinfo.xls and hydratecpa.xls spreadsheets useful. These have a restricted
component list (gases and gas condensates) but offer a choice of fluid and salt
model and a wider choice of caclulations.
Case studies - chemical
equilibria
Introduction
Most thermodynamic simulation in process engineering centres on the need to
calculate phase equilibria for separation processes, especially distillation.
However chemical equilibria is another area where thermodynamic information
can be exploited to make predictions about chemical processes.
The chemical reaction module in Multiflash is a utility for performing
simultaneous phase and chemical equilibrium calculations. It can handle
equilibria involving combinations of one gas phase, one liquid phase and any
number of pure solids.
The chemical reaction module does not rely on reaction schemes. You do not
need to specify any reaction mechanism but only list all the possible products
and reactants.
The applications are many and varied but a sample is discussed here
Xylene isomerisation
To start with a very simple example, select ortho-, meta- and para-xylene from
the INFODATA fluids bank.
Select RKS using the route Select/Model set/Equations of State/RKS. The
model set will be used to predict the phase properties and any of the cubic
equation of state models would be acceptable for this case study.
Enter a temperature of 575K and a pressure of 10 bar (remember to set the
pressure and temperature units correctly).
Click on the Chemical reaction button,

The mixture will be in the gas phase. You may ignore the warning message. All
model sets and model configuration files include phase descriptors for several
phases to give the user greatest flexibility. However, the chemical reaction
module is limited to one gas and one liquid phase, hence the warning message
and the ?CONVERGED message. If you use the problem setup file, xylene.mfl,
only one liquid phase is defined and the warning message will not appear. Also,
the calculation will be reported as converged.
Input any composition for the mixture provided there is a positive amount for
each xylene.
User Guide for Multiflash for Windows Case studies - chemical equilibria 243
At the same conditions the ratios of the three xylenes will remain the same.
If you reduce the temperature to 300K and the pressure to 1 bar the mixture will
be in the liquid phase. The equilibrium concentrations of the three xylenes are
slightly, but not significantly, different and again are unaffected by the input
compositions
Steam cracking of ethane

This case study to investigate the steam cracking of ethane is effectively a study
of two competing reactions
2H2O + C2H6 = 2CO + 2H2O
4H2O + C2H6 = 2CO2 + 7H2
You do not have to specify the reaction schemes only the products and reactants.
Therefore, you should
Select ethane, water, hydrogen, carbon monoxide and carbon dioxide from
INFODATA
In the drop down table under Composition enter 2 moles of water and 1 mole
of ethane
Select an equation of state model, e.g. RKS
Set the temperature to 1000K and the pressure to 1e5 Pa.
For this calculation it may also be useful to change the output from fractions to
amounts, see Changing units on page 152.
244 Case studies - chemical equilibria User Guide for Multiflash for Windows
Click on the chemical reaction button,
Under these conditions 4.96 moles of hydrogen, 1.974 moles of carbon
monoxide and 0.00668 moles of carbon dioxide are produced.
Vary the ratio of water to ethane and note the increase in the amounts of carbon
dioxide as the ratio increases.
You can look at the enthalpy changes for the reactions by carrying out a simple
P,T flash to obtain the enthalpy of the reactants and the chemical P,T reaction
flash to see the enthalpy of the products.
User Guide for Multiflash for Windows Case studies - chemical equilibria 245
Appendix - Multiflash
Commands
Introduction
The Multiflash command language is common to all Multiflash implementations
- DOS, Excel, VB etc. A complete list of all commands and information on how
to use them is contained in the Multiflash Command Reference manual.
In the Windows version the use of commands has largely been replaced by
menus and icons. However, not all the facilities available in the command
processor version of Multiflash have been incorporated as menu options in the
current version of Multiflash for Windows. An example might be reverting to a
previous version of the Infochem BIP databank to maintain backward
compatibility. To allow you full access to all Multiflash facilities a Tools
command option is available, see Tools on page 35, which allows you to enter
a command and apply this in the Windows version.
Commands are also used to specify problems in problem setup files. If the set
up file is created by saving a problem specified interactively then the appropriate
commands will be transferred automatically to the set up file.
When you may need to use commands

The menu options available in Multiflash will allow you to specify and solve
most problems. However, some of the areas where commands let you supply or
display additional information, supplement or amend menu options or carry out
additional calculations are:
Defining models
Supplying an external file of BIPs
Defining phase descriptors and key components
Defining models
The standard thermodynamic and transport property models available in
Multiflash are specified in the model sets and model configuration files supplied.
However, you may wish to set up your own model definition, for example you
may wish to use an activity style mixing rule with an equation of state model.
You may also wish to group together different models to describe different
User Guide for Multiflash for Windows Appendix - Multiflash Commands 247
properties, such as using an equation of state to describe the properties of a
refrigerant mixture but defining the density in terms of ideal mixing.
In general the MODELS command defines a thermodynamic or transport
property model for mixtures. The command has the format:
MODEL model_id MF_model_name [Model_options]
where
1. model_id is a user-defined name that will be used to refer to the
particular combination of the property model and options specified.
2. MF_model_name is the Multiflash name for the basic model. The
list of recognised models is given below together with the
applicable options.
3. Model_options are additional keywords that describe model
variants, references to other, previously-defined, models or
references to the source of binary interaction parameters.
Any .mfc file will provide an example of how to set up a model definition.
Supplying an external file of BIPs

We supply binary interaction parameters, for light gases and hydrocarbons for
use with the cubic equations of state from the OILANDGAS databank and for
activity coefficient models from INFOBIPS or INFOLLBIPS. If you have
interaction parameters available for other binary pairs and other models you may
wish to supplement or overwrite those stored in Multiflash. The Tools/BIPs
facility has been supplied to allow you to do this easily without the need for
commands and to save any changes by saving the problem setup file. However,
if you wish to store a preferred set of BIPs and to overwrite the stored BIPs
every time you run Multiflash it may be easier to set up your own input file.
You can then overwrite our BIPs by loading this file or including it as part of
your problem setup. In this case it may be easier to construct the file using
Multiflash commands.
The command for setting up a bipset takes the form
bipset, bipset_name number of BIPs for model, degree of temperature
dependence, name of components for binary pair, values for BIPs;
e.g.
bipset PRBIP 1 constant methane butane 0.005;
bipset WILSONBIP2 2 constant acetone water 6139
1450;
bipset NRTLBIP3 3 linear methanol water .22 4.4e-3
.30 -6.6e-3 .003 0.0
Other examples are provided in Supplementing or overwriting BIPs on page
78.
N.B. You must reload this BIP file every time you change the model as one of
the commands when a model is loaded removes existing bipsets.
Defining phase descriptors and key components

Now that you can define the phases to be considered as part of the model
definition the need to define or erase phase descriptors using Tools/Command
should be reduced. However, it may still occur.
248 Appendix - Multiflash Commands User Guide for Multiflash for Windows
A phase descriptor (PD) contains all the information required to identify a phase
and to retrieve its thermodynamic properties. A PD must be specified for each
possible phase that Multiflash is to consider. The PD command is used to define
a phase descriptor (PD). To exclude the formation of a particular phase type, e.g.
gas, the corresponding PD should be omitted or erased. The command has the
format:
PD pd_id phase_type model_identifiers
or
PD pd_id erase
The following table gives the valid options and settings:
command description notes
parameter
pd_id user-defined name that will any unique alphanumeric
be used to refer to the string, e.g. liquid1
particular instance of phase
type and associated models
phase_type a keyword that defines the 1. gas, vapor and vapour are
phase type, valid settings are: synonyms.
condensed 2. condensed means a pure
gas solid phase.
hydrate 3. solidsolution means a
liquid mixed solid phase
solidsolution
vapor
vapour
model_identifiers identifiers for up to six 1. the model identifiers are
models that will be used to the user-defined names
evaluate the thermodynamic associated with the models
and transport properties of (see description of
the phase. Models for the MODELS command)
following properties may be 2. at least one
specified in the order given: thermodynamic model must
1. fugacity (K-values) be defined (the same model
2. volume/density (optional) is then used for all
3. enthalpy/entropy thermodynamic properties)
(optional) 3. transport property models
4. viscosity (optional) need only be defined if
5. thermal conductivity output of these properties is
(optional) required
6. surface tension (optional)
erase erases (removes) the PD 1. the pd_id must have been
from the list of PDs available previously defined
for Multiflash 2. all information associated
with the PD is lost
The standard model sets and model configuration files include four phase
descriptors for GAS, LIQUID1, LIQUID2 and WATER. If you use the
Select/Freeze-out components option to apply the freeze-out model, see The
Freeze-out model on page 70, a phase descriptor will be automatically
generated from the component name. However, you can change this name using
the phase descriptor command.
You may wish to erase a phase descriptor to limit the number of phases
considered when solving a flash calculation, see Troubleshooting - flash
calculations on page 147.
The KEY command is used to define a key component for a PD. A key
component helps to identify a particular phase when two or more PDs would
otherwise be indistinguishable. It is not necessary to define a key component
unless a flash calculation needs to identify phases uniquely (e.g. a search for a
particular phase fraction). The command has the format:
KEY pd_id key_component_id
or:
KEY pd_id not key_component_id
pd_id is a previously-defined phase descriptor name.

key_component_id is the name of the component which is used to identify
the phase. The rule used is that the key component should be present in the phase
to the maximum amount relative to the total mixture composition. If the
250 Appendix - Multiflash Commands User Guide for Multiflash for Windows
component name is preceded by the keyword not , this means that the
component should be present in the minimum relative concentration.
The model sets and model configuration files supplied identify one liquid phase
as having water as the key component and the other two liquid phases in terms of
not being the water phase. There may be a case where you would wish to
allocate a key component to one of these, e.g.
Key liquid2 CO2;
or
Key liquid1 heaviest
C
Calculate 25
Calculating asphaltene flocculation conditions 215
Calculating the bubble point curve 164
Index Calculating the dew point curve 165

Calculating the water dew point line 167
Calculating wax appearance temperature (WAT) 206
Calculating wax precipitation 210
Calculation output 142
Calculations 3, 115
seeFlash calculations 115
Calculations with inhibitors 197
Can hydrates form at given P and T ? 198
CAPE-OPEN Interface 150
Carry out an isothermal flash 15
A Carrying out the flash calculation 17
Case studies 4, 11, 50, 155, 163, 171, 177, 185, 189,
Activity coefficient equations in Multiflash 35 205, 211, 229, 243
Activity coefficient methods 34 Asphaltenes 50, 211
Activity coefficient models 34 Chemical equilibria 243
see Models 34 Combined solids 229
Activity coefficients 143 Hydrate formation and inhibition 189
Activity model worksheets 236 Phase equilibria 163
Adding a component 68 Polymers 185
Adding water to the system 167 Pure component data 155
Additional calculations 14, 18 PVT Analysis 171
Additional fluid information 92 Refrigerants 177
Advanced Equation of state options 31 Tutorial 11
Analysis method 89 Wax 205
Asphaltene 9 Change the composition 15
Asphaltene flocculation 229 Change the enthalpy 15
Asphaltene with gas injection 240 Change the pressure 14
Asphaltenes 41, 50, 211, 240 Changing the default input and output units 137
Case study 50, 211 Changing units in a problem setup file 136
Defining Asphaltene model 50 Changing units interactively 136
Model 41 Characterisation 96
AYCONFIG.DAT 84, 139 Chemical equilibrium 2, 116, 131, 133, 134, 243
Azeotropes 183 Case study 243
Troubleshooting 134
B Chemreact 2, 116, 133
Choice of Analysis method 219
Benedict-Webb-Rubin-Starling (BWRS) equation of Chung-Lee-Starling model 43
state 33 Clearing previous problems 15
Benedict-Webb-Rubin-Starling model 33 Combined solids 229
Binary interaction parameters 53, 54, 57, 58 Combined Solids Model 50
Displaying values 54 Commands 4, 27, 247
Supplementing and overwriting BIPs 57 Appendix 247
Temperature dependence 54 Tools/Command option 27
Units 53 Component cannot be found 84
BIP databank 59 Component list 89
BIP set 55 Components 3, 9, 61, 63, 64, 65, 66, 67, 68, 69, 71,
Names 55 83, 155
BIPs 8, 53 Adding a component to a stream 68
see Binary interaction parameters 53 Condensed components 63
BIPs available in Multiflash 54 Databanks 61
BIPs not displayed 59 Defining components in stream 64
Black Oil Analysis 8, 95, 176 Deleting a component from a stream 69
Bubble point 118 DIPPR 61
Displaying pure component data 155
INFOCOND 63
User Guide for Multiflash for Windows Index 253

Inserting a component in a stream 69 Defining the components 16
Maximum number in stream 64 Defining the fixedphase flash 120
Normal components 61 Defining the hydrate models 189
Properties of normal components 61 Defining the model from the menu 44
Replacing a component in a stream 69 Defining the problem interactively 155
Selecting by formula 67 Defining the wax model 205
Selecting by name 66 Dew point 118
Selecting by scrolling through list 65 Dialogue boxes, text boxes, tab controls, drop-down
Selecting by substring 68 tables and menus 26
Selecting components 65 Diffusion coefficients 44
Synonyms of components 66 Diffusivity 8
Troubleshooting 83 DIPPR 61
User defined 71 Documentation 2
Compositions 17, 111, 112, 135, 136, 142 Dortmund Modified UNIFAC 8
Amounts and fractions 112, 135, 136, 142 Dortmund Modified UNIFAC method 36
Specifying compositions 111 Dortmund Modified UNIFAC model 36
Condensed components 63
INFOCOND 63 E
Conditions 111, 112, 113
Conditions section of main window 111 Edit 24
Specifying compositions 111 Entering BIPs 181
Specifying enthalpy 113 Enthalpy 113
Specifying entropy 113 Specifying for isenthalpic flash 113
Specifying internal energy 113 Entropy 113
Specifying pressure 112 Specifying for isentropic flash 113
Specifying temperature 112 Equation of state method 30
Specifying volume 112 Equations of State 30
Troubleshooting 113 see Models 30
Configuration files 24, 44, 46, 84, 137, 139 Equations of state provided in Multiflash 30
AYCONFIG.DAT 84, 139 Error messages 144
MFCONFIG.DAT 137 Errors 51, 58, 83, 113, 131, 134, 137, 142, 144, 146
Model configuration files 24, 44, 46 Convergence 142
Consider all types of solution 133 Messages 144
Corresponding states (CSM) model 34 Troubleshooting 51, 58, 83, 113, 131, 134, 137, 146
Coutinho wax model 206 Eutectics 184
CPA model 203 Examples 11, 50, 155, 163, 189, 205, 211, 243
CSM 34 Case studies 50, 155, 163, 189, 205, 211, 243
Reference fluids 34 Tutorial 11
Cubic plus association (CPA) model 32 Exiting Multiflash 21
Current settings 145
Display 145 F
Cut and paste 10
Files 12, 13, 19, 21, 24, 44, 46, 84, 137, 139, 140,
147, 158
D AYCONFIG.DAT 84, 139
Data Availability 220 Configuration file 84, 137, 139
Data input 185 Loading a model configuration file 44, 46
Databank configuration file 84, 139 Loading problem setup files 13
Databank not found 83 MFCONFIG.DAT 137
Databank not licensed 84 Model configuration (mfc) files 24, 44
Databanks 9, 61, 63 Output file 139, 140
DIPPR 61 PIPESIM PVT file 147
INFOCOND 63 Problem setup (mfl) files 12, 19, 158
INFODATA 61 Saving a problem setup file 19
Define Input Conditions 17 Saving results in an output file 21
Defining a mixture (stream) in Multiflash 64 Fitting pure component properties 9
Defining a problem in Multiflash 12 Fixed phase fraction flash 118
Defining models 247 Flash calculations 113, 115, 116, 117, 118, 121, 131,
Defining petroleum fractions 87 133
Defining the asphaltene model 212 Bubble points 118
254 Index User Guide for Multiflash for Windows

Chemical equilibrium 133 I
Definition of a flash calculation 115
Dew point 118 Ice model 190
Fixed phase fraction flash 118 Ideal gas equation of state 30
Isenthalpic flash 117 Ideal solution model 35
Isentropic flash 117 Including a petroleum fraction 168
Isochoric flash 118 Incorrect path 51
Isothermal (P,T) flash 117 INFOCOND 63
List of available flash calculations 116 Condensed components 63
Retrograde flash calculations 121 INFODATA 61
Starting estimates 133 Infochem fluids databank 61
Troubleshooting 131 Inhibition 39, 200, 201
Type of solution 121 Hydrate inhibition case study 200
Flory Huggins model 35 Model for hydrate inhibition 39
Flory-Huggins 7, 35 Salt inhibition case study 201
Fluid characterisation 8 Inhibitor Calculator 79, 198
Fluid composition 92 Inhibitor modelling 39
Fluid phase model 190 Input 3
Font 140 Input Conditions 3, 111
Fonts 146 seeConditions 111
Freeze-out model 37 Input data 211
Fugacity coefficients 143 Input files 12, 13, 19, 23, 158
Fuller model 44 Loading a problem setup file 13
Problem setup files 12, 19, 158
Saving a problem set up file 19
G Writing a problem setup file 158
Gas injection 224 Installation 4
Gas phase models for activity coefficient methods 36 Interface to other programs 115, 147, 161, 183
Groups not available for UNIFAC model 52 Excel spreadsheet 115, 161, 183
PIPESIM 147
Interfaces 10
H Internal energy 113
Hayduk Minhas method 44 specifying as a flash condition 113
HELP 4, 26, 144, 151 Introduction 1, 7, 11, 23, 29, 61, 87, 111, 115, 135,
How to exit the program 21 139, 147, 151, 155, 163, 189, 205, 211, 229,
How to specify models in Multiflash 44 235, 243, 247
Hydrate 39, 48, 79, 190, 198 Isenthalpic flashes 117
Inhibitor Calculator 79, 198 Isentropic flashes 117
Nucleation model 39, 48, 190 Isochoric flashes 118
Hydrate calculations with Multiflash 191 Isothermal (P,T) flash 117
Hydrate dissociation pressure at a given temperature
199 K
Hydrate dissociation temperature at a given pressure
199 Key components 119, 248
Hydrate formation and dissociation pressure at given
temperature 195 L
Hydrate formation and dissociation temperature at
given pressure 193 LCVM equation of state 33
Hydrate formation temperature at given pressure 194 LCVM model 33
Hydrate inhibitors 79 Lee-Kesler-Plcker (LKP) equation of state 33
Hydrate model 190 Lee-Kesler-Plcker (LKP) model 33
Hydrate phase boundary 196, 199 Limit the number of phases 132
Hydrates 37, 39, 189, 196, 200, 201, 241 Liquid-liquid equilibria 182
Case study 189 Loading an existing problem file 12
Hydrate inhibition case study 200 Loading files 13, 44, 46
Hydrate inhibitor model 39 Loading a model configuration file 44, 46
Hydrate model 37 Loading problem setup files 13
Hydrate salt inhibition case study 201 Loading hydrate models 47
Phase boundary 196 Log file 21, 139, 140
Hydrates, Waxes and Asphaltenes 231 Saving the log file 21
Lorentz-Bray-Clark model 43

M Peneloux density correction 31
Peng Robinson (PR) 30
Macleod-Sugden model 44 Polymer 32
Mass fraction flash 118 PSRK 33
Match bubble point 238 Redlich-Kwong (RK) 31
Matching 9, 102, 105, 106, 222 Redlich-Kwong-Soave (RKS) 31
Asphaltene flocculation 222 Regular Solution 35
Dew and bubble points 102 Salinity model 40
Liquid viscosity 106 Selecting model 44
Wax Appearance Temperature 105 Selecting model set 16
Matching using petroleum fraction properties 102 Selecting new model 47
Maximum water content allowable before hydrate Solid models 37
dissociation 196 Surface tension 44
Menu options 24 Transport property 42
mfc files 24, 44, 46 Troubleshooting 51
MFCONFIG.DAT 137 Twu 42
mfl files 12, 19, 158 UNIFAC 36
Mixing rules 31, 43, 44 UNIQUAC 35
Liquid thermal conductivity 43 Viscosity 42
Liquid viscosity 43 Wax 41
Surface tension 44 When to use activity methods 36
Vapour thermal conductivity 44 When to use BWRS 34
Vapour viscosity 43 When to use CPA 32
Model configuration files 24, 44, 46 When to use CSM 34
Model is not licensed 52 When to use cubic equations of state 31
Model set 44, 46 When to use equation of state methods 30
Selecting the model 44 When to use LCVM 33
Modelling a polar mixture. 179 When to use LKP 33
Models 3, 7, 16, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, When to use PC-SAFT 32
40, 41, 42, 43, 44, 47, 48, 51, 53, 190 When to use PSRK 33
Advanced equations of state 31 Wilson A 35
Asphaltenes 41 Wilson E 35
Benedict-Webb-Rubin-Starling (BWRS) 33 Models for solid phases 36
Binary interaction parameters (BIPs) 53 Multiflash 1, 2, 11, 21, 23, 29, 61, 111, 116, 135, 139,
Chung-Lee-Starling 43 147, 155
Corresponding states (CSM) 34 Calculations 116
Costald model 42 Case studies 155
Cubic plus association (CPA) 32 Components 61
Diffusion coefficients 44 Conditions 111
Dortmund Modified UNIFAC 36 Exiting the program 21
Flory Huggins 35 Input 23
Freezeout model 37 Interfaces to other programs 147
Fuller model 44 Models 29
Gas phase models 36 Output 139
Hayduk Minhas method 44 Overview 1
Hydrate model 37 Phase equilibrium 1
Hydrate nucleation model 39, 48, 190 Simple tutorial 11
Ideal gas 30 Software system 2
Ideal solution 35 Starting the program 11
LCVM 33 Units 135
Lee-Kesler-Plcker (LKP) 33 Multiflash configuration file 137
Liquid density model 42 Multisolid model 205
Lorentz-Bray-Clark 43
Macleod-Sugden 44
Mixing rules 31 N
Model configuration file 44 Naming the components 59
Model definitions 29 New Features 7
Model set 44 New Features and Changes in Version 3.3 3
NRTL 35 No information on the amount of asphaltene in the oil
PC-SAFT 32 220
Pedersen 42

No reservoir or flocculation conditions 222 Phase labels 146
No reservoir pressure 221 Phase names 119, 146
No resin - asphaltene ratio 221 Phase types 118
Normal components 61 Selecting phases 45
DIPPR 61 Solid phases 36
INFODATA 61 Types of phase 1
Properties of normal components 61 Physical properties of a pure component 155
Notes 235 PIPESIM 147
n-Paraffin distribution 94 PVT file 147
NRTL equation 35 Plot the phase envelope 132
NRTL model 35 Plots 124
Nucleation 193 H, S, U, V phase boundaries 124
Nucleation model 39, 48, 190 Phase envelope 124
Number of BIPs for the model 58 Plotting 8
Number of BIPs related to any model 53 Polar systems 179
Polymers 32, 185
O Case study 185
PC-SAFT model 32
Obtaining properties from Pure component Data Presence of water 99
option 159 Pressure 17, 112
Oil and gas systems 163 Specifying as an input condition 112
OLGA 148 Printing 20
On-line help 151, 154 Output 20
Order of components 58 Printing the output 20, 141
Other flash calculations 169 Problem setup file 12, 13, 19, 158
Other flash calculations with hydrates 196 Loading a problem setup file 13
Other thermodynamic models 42 Saving a problem setup file 19
Output 3, 21, 130, 139, 140, 146 Writing a problem setup file 158
Level of physical property output 130 Problem setup files 12
Saving the output file 21 Problems when matching 109
Troubleshooting 146 Properties 9, 61, 130, 155
Writing the results to a file 139, 140 Displaying pure component properties 155
Output to Excel 144 Level of physical property output 130
Overview 2 Physical property databanks 61
Provide a key component 133
P PSRK equation of state 33
PSRK model 33
PC-SAFT 7 PVT Analysis 88, 99, 171, 238
PC-SAFT equation of state.. 32 Case study 171
PC-SAFT model 32 Saving an analysis 99
Pedersen Model 42 Troubleshooting 99
Peng-Robinson (PR) model 30
Peng-Robinson equation of state) 16, 30
Penneloux density correction 8
R
Petroleum Fractions 3, 61, 63, 87, 97, 99, 101, 108 Redlich-Kwong (RK) and Redlich-Kwong-Soave
Defining a petroleum fraction 63, 87, 99 (RKS) equations 31
Editing petroleum fraction data 101 Redlich-Kwong (RK) model 31
Splitting 97 Redlich-Kwong-Soave (RKS) model 31
Troubleshooting 108 Refrigerants 177
Phase descriptors 23, 46 Case study 177
Phase diagram 121 Regular Solution 7
Phase envelope 18, 124, 130, 132, 146, 166 Regular Solution model 35
Customising 130 Regular Solution theory 35
Phase envelope output 144 Results 13, 20, 24, 130, 139
Phase envelope plotting 10 Level of physical property output 130
Phase names 119 Printing the results 20, 24
Phases 1, 23, 36, 45, 46, 118, 119, 121, 132, 146, 190 Results window 139
Example of a phase diagram 121 Saving the results in a file 20, 24
Example of a phase envelope 132 Retrograde 122
Phase descriptors 23, 46 Retrograde condensation 122

Retrograde dew point 122 Temperature 112
Running Multiflash 3 Specifying as an input condition 112
Temperature dependence of BIPs 54
S The Freeze-out model 48
The output does not include everything expected 146
Salinity model 40 Thermal conductivity 43
Salt calculator 81 Models 43
Salt inhibition 201 Titration 224
Hydrate salt inhibition case study 201 Tolerance calculations 122
SARA Analysis 96 Too many components in the mixture 85
Saving a problem setup 19 Toolbar buttons 26
Saving files 19 Tools 25
Saving a problem setup file 19 Total amount of fluid 96
Saving results 139, 140 Transport properties 42, 43, 44, 130
Writing the results to a file 139, 140 Displaying transport property values 130
Saving the output 20 Models 42
Searching for components 65, 66, 67, 68 Surface tension 44
By formula 67 Thermal conductivity 43
By name 66 Viscosity 42
By scrolling through list 65 Transport property models 42
By substring 68 Troubleshooting 51, 58, 83, 99, 113, 131, 134, 137,
Identifying synonyms 66 146
Select 25 Binary interaction parameters 58
Select components by formula 67 Calculations 131
Select components by name 66 Chemical reaction 134
Select components by scrolling through a list 65 Components 83
Sensitivity of calculations to variation in input data Models 51
219 Output 146
Sensitivity to characterisation 99 PVT Analysis 99
Setting up a problem interactively 15 Units 137
Show functions 145 Tutorial 11
Simple tutorial 3 Twu Model 42
Soave-Redlich-Kwong (RKS) model 31
Solids.xls, Solids31.xls and Solids32.xls 237
U
Specifying enthalpy, entropy and internal energy 113
Specifying the data source 64 UNFACFIT.xls 235
Splitting 97 UNIFAC 236
Stability analysis 1, 142 UNIFAC method 36
Starting a new problem 21 UNIFAC model 36
Starting estimate for flash calculations 124, 133 UNIQUAC 35
Starting Multiflash 11 UNIQUAC equation 35
Steam cracking of ethane 244 Units 3, 10, 53, 58, 135, 137
Stream types 76 Default units 135
Supplementary information 8 Selecting units 135
Supplementing or overwriting BIPs 56 Troubleshooting 137
Supplying an external file of BIPs 248 Units for BIPs 53, 58
Surface tension 44 Working units 135
Models 44 Updates 7
Synonyms 66 Use the P,T flash 132
Component synonyms 66 User defined components 71
User Guide 151
T Using INFOBIPS 179
Table 26
V
Tables 10
Tabular output 115, 147 Vapour-liquid-liquid equilibria 183
Excel interface 115 Viewing and editing pure component data. 69
PSF file for HTFS programs 147 Viscosity 42, 106
PVT file for PIPESIM 147 Matching liquid viscosity 106
Technical support 154 Models 42

VLEFIT.xls 237
Volume 112
Specifying as a flash condition 112
Volume fraction flash 118
W
Warnings 142, 144, 183, 243
Additional phases 183
Chemical reaction 243
Convergence 142
Water cut 96
Wax 41, 49, 105, 205, 239
Case study 205
Coutinho Model 41
Defining Wax model 49
Matching WAT 105
Multisolid Model 41
Wax and Asphaltene precipitation 230
Wax Content 95
Website support 154
What is a model? 29
What the model definition means 46
What types of model are available? 29
When to use activity coefficient models 36
When to use cubic equations of state 31
When to use equation of state methods 30
When you may need to use commands 247
Will hydrates form at given P and T ? 192
Wilson A equation 35
Wilson A equation, 35
Wilson A model 35
Wilson E equation 35
Wilson E model 35
Write to Excel 130
Writing the results to a file 140
X
Xylene isomerisation 243

Multiflash For Windows

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User Guide for

Multiflash for Windows

Infochem Computer Services Ltd

Infochem Computer Services Ltd

New Features and Changes in Version 3.3 7

User Guide for Multiflash for Windows Contents iii

iv Contents User Guide for Multiflash for Windows

User Guide for Multiflash for Windows Contents v

Calculations (flashes) 115

vi Contents User Guide for Multiflash for Windows

Case studies - Pure component data 155

Case studies - Phase equilibria 163

Case studies - Hydrate dissociation, formation and inhibition 189

User Guide for Multiflash for Windows Contents vii

Case studies Wax deposition 205

Case studies Asphaltene flocculation 211

Case studies Combined solids 229

Case studies Excel spreadsheets 235

Case studies - chemical equilibria 243

viii Contents User Guide for Multiflash for Windows

User Guide for Multiflash for Windows Contents ix

Multiflash phase equilibrium utility

User Guide for Multiflash for Windows Overview 1

Multiflash Software System

2 Overview User Guide for Multiflash for Windows

User Guide for Multiflash for Windows Overview 3

Appendix - Multiflash Commands

4 Overview User Guide for Multiflash for Windows

Penneloux density correction

Black Oil Analysis

Fitting pure component properties

Cut and paste

The Multiflash Main Window should then appear.

User Guide for Multiflash for Windows Simple Tutorial 11

Defining a problem in Multiflash

Problem setup file

Loading an existing problem file

12 Simple Tutorial User Guide for Multiflash for Windows

Clicking on Load problem setup button .

This will activate the Load Multiflash File Dialogue box,

which will show a list of available setup files (*.mfl) contained in

2. Scroll to C4C5.mfl, which will now be highlighted, and either

User Guide for Multiflash for Windows Simple Tutorial 13

Change the pressure

2. Click on P,H flash button

14 Simple Tutorial User Guide for Multiflash for Windows

Change the enthalpy

Change the composition

Carry out an isothermal flash

2. Click on the P,T flash button

Setting up a problem interactively

Clearing previous problems

User Guide for Multiflash for Windows Simple Tutorial 15

Click on OK to return to the Select Models dialogue box. Click on Close to

Defining the components

16 Simple Tutorial User Guide for Multiflash for Windows

Define Input Conditions

Carrying out the flash calculation

Click on the bubble point at fixed pressure button,

User Guide for Multiflash for Windows Simple Tutorial 17

1. Clicking on the phase envelope button or clicking on the

The phase envelope will be displayed in a separate window.

18 Simple Tutorial User Guide for Multiflash for Windows