Manual Multiflash 4.x PDF

User Guide for
Multiflash for Windows

Infochem/KBC Advanced Technologies plc
Version 4.4
February 2014

Unit 4, The Flag Store
23 Queen Elizabeth Street
London SE1 2LP
Tel: +44 [0]20 7357 0800
Fax: +44 [0]20 7407 3927
e-mail: software@kbcat.com
This User Guide and the information contained within is the copyright of Infochem Computer Services Ltd.

Unit 4, The Flag Store
London SE1 2LP, UK
Tel:+44 [0]20 7357 0800
Fax:+44 [0]20 7407 3927
e-mail:software@kbcat.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
The Multiflash GUI ..................................................................................................... 1
Multiflash Software System....................................................................................................... 1
Document Organisation ............................................................................................................. 2
New Features and Changes in Version 4.4 and 4.3 ..................................................... 2
New Features and Changes in Version 4.2 .................................................................. 2
Running Multiflash...................................................................................................... 2
HELP ........................................................................................................................... 3
Case studies ................................................................................................................. 3
Appendix - Multiflash Commands .............................................................................. 3
Installation ................................................................................................................................. 3
New Features and Changes in Version 4.4 and 4.3 5

Introduction ............................................................................................................................... 5
Models ....................................................................................................................................... 5
Huron-Vidal-Pedersen mixing rule.............................................................................. 5
Sutton Model for surface tension................................................................................. 5
LBC ............................................................................................................................. 5
Salt component ............................................................................................................ 5
High accuracy reference eos for water-ammonia binary system ................................. 6
New high accuracy reference eos ................................................................................ 6
Activity Coefficient models......................................................................................... 6
Performance enhancements ......................................................................................... 6
Phase key components................................................................................................. 6
Windows GUI............................................................................................................................ 6
PVTSim import tool .................................................................................................... 6
Models tab ................................................................................................................... 6
Inhibitor calculator ...................................................................................................... 6
Surface tension ............................................................................................................ 7
Petroleum Fraction Input Table................................................................................... 7
Tables......................................................................................................................................... 7
OLGA tables................................................................................................................ 7
Interfaces ................................................................................................................................... 7
Excel Interface............................................................................................................. 7
CAPE-OPEN ............................................................................................................... 7
Databanks .................................................................................................................................. 7
Infodata........................................................................................................................ 7
DIPPR.......................................................................................................................... 7
New Features and Changes in Version 4.2 9

Introduction ............................................................................................................................... 9
Models ....................................................................................................................................... 9
CSMA model............................................................................................................... 9
Mercury ....................................................................................................................... 9
Poynting correction ..................................................................................................... 9
Activity coefficient model for gas phase ..................................................................... 9
LBC viscosity model ................................................................................................. 10
User Guide for Multiflash for Windows Contents  iii

Binary Interaction Parameters ................................................................................................. 10
Multiflash phase equilibrium algorithm................................................................................... 10
Flash calculations..................................................................................................................... 10
Databanks ................................................................................................................................ 10
Infodata...................................................................................................................... 10
Windows GUI.......................................................................................................................... 11
PVTSim import tool .................................................................................................. 11
Reid vapour pressure ................................................................................................. 11
Liquid dropout and Wax precipitation curve............................................................. 11
New icon for Asphaltene precipitation curve ............................................................ 11
Phase envelopes for solids......................................................................................... 11
Hydrate models.......................................................................................................... 11
Inhibitor calculator .................................................................................................... 11
PVT Analysis ............................................................................................................ 11
Retrograde Dew Point ............................................................................................... 11
Calculation options.................................................................................................... 11
Usability .................................................................................................................... 12
Tables....................................................................................................................................... 12
OLGA tables.............................................................................................................. 12
Multiflash Excel Interface ....................................................................................................... 12
Joule-Thompson coefficient ...................................................................................... 12
Getting Started 13
Starting Multiflash ................................................................................................................... 13
Multiflash Main Window......................................................................................................... 13
Input section .............................................................................................................. 14
Conditions ................................................................................................................. 14
Fluid identification .................................................................................................... 14
Compositions............................................................................................................. 14
Results window ......................................................................................................... 14
Menu options............................................................................................................. 14
The Toolbar ............................................................................................................... 18
Defining a problem in Multiflash ............................................................................................ 18
Loading an existing problem file ............................................................................................. 18
Loading a problem setup file ..................................................................................... 18
Calculations ............................................................................................................... 19
The results ................................................................................................................. 19
Additional calculations .............................................................................................. 20
Setting up a new problem ........................................................................................................ 21
Clearing previous problems....................................................................................... 21
Defining the components........................................................................................... 21
Defining the models .................................................................................................. 22
Set Input Conditions .................................................................................................. 23
Carrying out the flash calculation.............................................................................. 23
Other calculations...................................................................................................... 24
Phase envelope .......................................................................................................... 24
Saving the problem setup......................................................................................................... 25
Backup file ................................................................................................................ 26
Loading a existing MFL file .................................................................................................... 26
Warning option for matching and PVT form........................................................................... 26
Printing the output ................................................................................................................... 26
Saving the output ..................................................................................................................... 27
How to exit the program .......................................................................................................... 27
Technical support..................................................................................................................... 28
Models 29
Introduction ............................................................................................................................. 29
What is a model? ..................................................................................................................... 29
What types of model are available? ......................................................................................... 29
iv  Contents User Guide for Multiflash for Windows

Equation of state models.......................................................................................................... 30
When to use equation of state methods ..................................................................... 30
Equations of state provided in Multiflash ................................................................................ 30
Ideal gas equation of state ......................................................................................... 30
Peng-Robinson equation of state ............................................................................... 30
Peng-Robinson 1978 (PR78) equation of state.......................................................... 31
Redlich-Kwong (RK) and Redlich-Kwong-Soave (RKS) equations......................... 31
Advanced Equation of state options .......................................................................... 31
When to use cubic equations of state......................................................................... 32
Cubic plus association (CPA) model......................................................................... 32
PSRK equation of state.............................................................................................. 32
ZJ (Zudkevitch-Joffe) model ..................................................................................... 33
PC-SAFT equation of state........................................................................................ 33
Lee-Kesler (LK) and Lee-Kesler-Plöcker (LKP) equations of state.......................... 34
Benedict-Webb-Rubin-Starling (BWRS) equation of state ....................................... 34
Multi-reference fluid corresponding states (CSMA) model ...................................... 35
IAPWS-95 ................................................................................................................. 35
Water-Ammonia ........................................................................................................ 35
Carbon Dioxide high-accuracy model ....................................................................... 36
GERG-2008............................................................................................................... 36
GERG-2008 (Infochem extension)............................................................................ 36
Activity coefficient methods.................................................................................................... 37
Activity coefficient equations in Multiflash .............................................................. 37
Gas phase models for activity coefficient methods ................................................... 38
When to use activity coefficient models.................................................................... 38
Models for solid phases ........................................................................................................... 39
Solid freeze-out model .............................................................................................. 39
Scaling and general freeze-out model........................................................................ 39
Modelling hydrate formation and inhibition.............................................................. 39
Modelling wax precipitation...................................................................................... 42
Modelling asphaltene flocculation............................................................................. 43
Other thermodynamic models ................................................................................... 43
Transport property models....................................................................................................... 44
Viscosity.................................................................................................................... 44
Thermal conductivity................................................................................................. 45
Surface Tension ......................................................................................................... 46
Diffusion coefficient.................................................................................................. 46
How to specify models in Multiflash....................................................................................... 47
Using the menu.......................................................................................................... 47
Loading a model from a .mfl file............................................................................... 48
Setting up preferred models in Multiflash ................................................................. 48
How to change a model ............................................................................................. 48
Models for solid phases ........................................................................................................... 48
Hydrates .................................................................................................................... 48
Pure solid phase......................................................................................................... 49
Waxes ........................................................................................................................ 50
Asphaltenes ............................................................................................................... 51
Combined Solids Model ............................................................................................ 52
Troubleshooting - models ........................................................................................................ 52
Model is not available ............................................................................................... 52
Groups not available for UNIFAC model ................................................................. 52
Binary interaction parameters .................................................................................................. 53
BIPs and models ........................................................................................................ 53
Temperature dependence of BIPs.............................................................................. 54
BIPs available in Multiflash ...................................................................................... 54
Viewing BIP values................................................................................................... 55
Units for BIPs............................................................................................................ 57
Supplementing or overwriting BIPs .......................................................................... 58
BIPs for CSMA and GERG mixing rule ................................................................... 59
Troubleshooting - BIPs............................................................................................................ 60
User Guide for Multiflash for Windows Contents  v

Units .......................................................................................................................... 60
BIP databank ............................................................................................................. 60
Differences between the PR Model in Multiflash and Aspen Hysys ....................................... 60
Components 63
Introduction ............................................................................................................................. 63
Normal components................................................................................................... 63
Petroleum fractions.................................................................................................... 65
Defining a mixture ................................................................................................................... 65
Specifying the data source......................................................................................... 66
Selecting components................................................................................................ 66
Adding, inserting, replacing and deleting components.............................................. 69
Viewing and editing pure component data ................................................................ 70
User-defined components ........................................................................................................ 72
Adding a user-defined component............................................................................. 72
Specifying data for a user-defined component .......................................................... 73
Models and input requirements ................................................................................. 74
Stream types ............................................................................................................................ 76
Hydrate inhibitors .................................................................................................................... 79
Inhibitor calculator: alcohols/glycols ........................................................................ 79
Salt calculator ............................................................................................................ 81
Troubleshooting - components ................................................................................................ 84
Databank not found ................................................................................................... 84
Databank not licensed................................................................................................ 85
Component cannot be found...................................................................................... 86
Too many components in the mixture ....................................................................... 87
Petroleum fluids 89
Introduction ............................................................................................................................. 89
PVT Lab Analysis input .......................................................................................................... 89
Component list .......................................................................................................... 91
Petroleum fluid composition ..................................................................................... 94
Molecular weight and specific gravity ...................................................................... 95
Total amount of fluid................................................................................................. 96
Water cut ................................................................................................................... 97
Total Wax Content .................................................................................................... 97
SARA Analysis ......................................................................................................... 97
Pseudocomponents .................................................................................................... 98
Characterisation......................................................................................................... 99
User Defined Cuts ................................................................................................... 100
Saving a PVT Analysis............................................................................................ 101
Black Oil Analysis ................................................................................................................. 101
Input data................................................................................................................. 102
Distillation curves .................................................................................................................. 102
TBP distillation........................................................................................................ 102
ASTM D86 distillation ............................................................................................ 104
PVT Lab Analysis input with n-paraffin analysis.................................................................. 105
n-Paraffin distribution ............................................................................................. 105
Characterisation....................................................................................................... 107
Estimated n-paraffin distribution............................................................................. 108
Troubleshooting – PVT Analysis........................................................................................... 109
Sensitivity to characterisation.................................................................................. 109
Presence of water..................................................................................................... 109
Defining petroleum fractions ................................................................................................. 109
Basic characterisation properties ............................................................................. 109
Other properties....................................................................................................... 110
Entering petroleum fractions ................................................................................... 110
Editing petroleum fraction data ............................................................................... 112
Deleting petroleum fractions ................................................................................... 112
vi  Contents User Guide for Multiflash for Windows

Problems defining a petroleum fraction .................................................................. 113
Delumping tool ...................................................................................................................... 113
How to use the delumping utility ............................................................................ 114
Matching using petroleum fraction properties ....................................................................... 116
Matching dew and bubble points............................................................................. 116
Matching Density/Volume ...................................................................................... 122
Matching wax data/WAT ........................................................................................ 123
Matching liquid viscosity ........................................................................................ 125
Matching vapour viscosity ...................................................................................... 126
Problems when matching ........................................................................................ 127
Petroleum Fluid Blending...................................................................................................... 127
Blending method ..................................................................................................... 128
Fluid file name......................................................................................................... 128
Fluid amounts .......................................................................................................... 129
Model definition ...................................................................................................... 129
Blending procedure ................................................................................................. 129
Example for blending .............................................................................................. 130
Example with waxy crudes...................................................................................... 132
Example with asphaltenic crudes ............................................................................ 133
Input conditions 137

Introduction ........................................................................................................................... 137
Specifying compositions........................................................................................................ 137
Specifying temperature, pressure and volume ....................................................................... 138
Specifying enthalpy, entropy and internal energy.................................................................. 139
Troubleshooting - input conditions........................................................................................ 139
Calculations 141
Introduction ........................................................................................................................... 141
The basis of a flash calculation.............................................................................................. 141
Flashes available in Multiflash .............................................................................................. 142
Isothermal (P,T) flash.............................................................................................. 142
Isenthalpic flashes ................................................................................................... 143
Isentropic flashes ..................................................................................................... 143
Isochoric flashes ...................................................................................................... 143
Bubble and dew point flashes.................................................................................. 143
Fixed phase fraction flashes .................................................................................... 144
Phase Envelopes ...................................................................................................... 148
Phase Envelopes for solids ...................................................................................... 157
Liquid dropout curve calculation............................................................................. 158
Hydrate calculations ................................................................................................ 159
Wax calculations ..................................................................................................... 159
Tolerance calculations ............................................................................................. 161
Reid Vapour Pressure .............................................................................................. 162
Property output in Multiflash................................................................................................. 164
Troubleshooting - flash calculations ...................................................................................... 165
Plot the phase envelope ........................................................................................... 166
Use the P,T flash ..................................................................................................... 166
Limit the number of phases ..................................................................................... 167
Consider all types of solution .................................................................................. 167
Provide a starting estimate....................................................................................... 167
Provide a key component ........................................................................................ 168
Units 169
Introduction ........................................................................................................................... 169
Default units .......................................................................................................................... 169
Changing units ....................................................................................................................... 170
Troubleshooting - units.......................................................................................................... 171
User Guide for Multiflash for Windows Contents  vii

Output 173
Introduction ........................................................................................................................... 173
The results window................................................................................................................ 173
Font........................................................................................................................................ 174
Writing the results to a file .................................................................................................... 174
Printing the output ................................................................................................................. 175
Calculation output.................................................................................................................. 175
Manipulating the Output.......................................................................................... 177
Phase Labelling...................................................................................................................... 178
Aqueous phase labelling.......................................................................................... 178
Enthalpy definition ................................................................................................................ 178
Activity Models ....................................................................................................... 179
Entropy definition .................................................................................................................. 180
Activity Models ....................................................................................................... 180
Errors and warning messages ................................................................................................ 181
Displaying status for current settings..................................................................................... 181
Troubleshooting - output ....................................................................................................... 181
The output does not include everything expected ................................................... 181
Phase labelling......................................................................................................... 182
Fonts ........................................................................................................................ 182
Interfaces with other programs 183

Introduction ........................................................................................................................... 183
Pipesim PVT files .................................................................................................................. 183
OLGA .................................................................................................................................... 184
OLGA hydrate file................................................................................................... 186
OLGA wax file ........................................................................................................ 186
Prosper PVT files................................................................................................................... 187
To generate the file.................................................................................................. 187
CAPE-OPEN Interface .......................................................................................................... 188
PVTSim CHC file import tool ............................................................................................... 189
Help 191
Introduction ........................................................................................................................... 191
On-line help ........................................................................................................................... 191
Help Topics ............................................................................................................. 191
Multiflash Error Codes ............................................................................................ 193
Check for Updates ................................................................................................... 193
About Multiflash ..................................................................................................... 194
Technical support................................................................................................................... 194
Case studies - Pure component data 197

Introduction ........................................................................................................................... 197
Physical properties of a pure component ............................................................................... 197
Defining the problem in Multiflash ......................................................................... 197
Obtaining properties from the Pure Component Data option .................................. 200
Excel interface ......................................................................................................... 202
Case studies - Phase equilibria 205

Introduction ........................................................................................................................... 205
Oil and gas systems ............................................................................................................... 205
Calculating the bubble point curve .......................................................................... 206
Calculating the dew point curve .............................................................................. 207
Phase envelope ........................................................................................................ 208
Adding water to the system ..................................................................................... 209
Including a petroleum fraction ................................................................................ 210
viii  Contents User Guide for Multiflash for Windows

Other flash calculations ........................................................................................... 212
PVT Analysis......................................................................................................................... 214
User defined carbon number cuts ............................................................................ 219
TBP curves .............................................................................................................. 221
Black Oil Analysis ................................................................................................................. 223
Delumping tool – Case study................................................................................................. 225
Refrigerant mixtures .............................................................................................................. 229
Polar systems ......................................................................................................................... 230
Modelling a polar mixture ....................................................................................... 230
Liquid-liquid equilibria ........................................................................................... 234
Vapour-liquid-liquid equilibria................................................................................ 235
Azeotropes............................................................................................................... 235
Eutectics .................................................................................................................. 236
Polymers ................................................................................................................................ 237
Data input ................................................................................................................ 237
Co-Polymers............................................................................................................ 239
Case studies - Hydrate dissociation, formation and inhibition 243

Introduction ........................................................................................................................... 243
Defining the hydrate models.................................................................................................. 243
Fluid phase model ................................................................................................... 244
Hydrate model ......................................................................................................... 244
Nucleation model .................................................................................................... 245
Ice model ................................................................................................................. 245
Scale model ............................................................................................................. 245
Phases ...................................................................................................................... 245
Hydrate calculations with Multiflash..................................................................................... 246
Will hydrates form at given P and T ?..................................................................... 246
Hydrate formation and dissociation temperature at given pressure......................... 247
Hydrate formation and dissociation pressure at given temperature ......................... 250
Hydrate phase boundary .......................................................................................... 251
Other flash calculations with hydrates..................................................................... 251
Maximum water content allowable before hydrate dissociation ............................. 251
Calculations with inhibitors ................................................................................................... 252
Can hydrates form at given P and T ?...................................................................... 252
Hydrate dissociation temperature at a given pressure ............................................. 254
Hydrate dissociation pressure at a given temperature ............................................. 254
Hydrate phase boundary .......................................................................................... 254
Amount of inhibitor required to suppress hydrates ................................................. 255
Salt inhibition .......................................................................................................... 256
Scale precipitation ................................................................................................................. 258
Case studies – Wax precipitation 260

Introduction ........................................................................................................................... 260
Defining the wax model......................................................................................................... 260
Calculating wax appearance temperature (WAT).................................................................. 261
Calculating wax precipitation ................................................................................................ 264
Case studies – Asphaltene flocculation 267

Introduction ........................................................................................................................... 267
Input data ............................................................................................................................... 267
Defining the asphaltene model .............................................................................................. 268
Asphaltene matching ............................................................................................... 270
Saturation P at reservoir T ....................................................................................... 272
Calculating asphaltene precipitation conditions .................................................................... 272
Sensitivity of calculations to variation in input data.............................................................. 276
Choice of Analysis method ..................................................................................... 276
Data Availability ..................................................................................................... 277
User Guide for Multiflash for Windows Contents  ix

No reservoir or precipitation conditions .................................................................. 280
Gas injection .......................................................................................................................... 282
Titration ................................................................................................................................. 283
Case studies – Combined solids 287

Introduction ........................................................................................................................... 287
Asphaltene precipitation ........................................................................................................ 287
Wax and Asphaltene precipitation ......................................................................................... 288
Hydrates, Waxes and Asphaltenes......................................................................................... 289
Case studies – Excel spreadsheets 293

Introduction ........................................................................................................................... 293
UNFACFIT.xls ...................................................................................................................... 293
Notes........................................................................................................................ 294
UNIFAC .................................................................................................................. 294
Activity model worksheets ...................................................................................... 294
VLEFIT.xls............................................................................................................................ 295
Solids.xls................................................................................................................................ 296
PVT Analysis .......................................................................................................... 296
Match bubble point.................................................................................................. 297
Wax ......................................................................................................................... 298
Asphaltenes ............................................................................................................. 299
Asphaltene with gas injection.................................................................................. 300
Hydrates .................................................................................................................. 301
Case study – Mercury partitioning 303

Introduction ........................................................................................................................... 303
Defining the mercury model .................................................................................................. 303
Calculating mercury partitioning and dropout ....................................................................... 304
Other calculations .................................................................................................................. 308
Distribution of mercury species ............................................................................................. 308
Appendix - Multiflash Commands 311

Introduction ........................................................................................................................... 311
Commands ............................................................................................................................. 311
When you may need to use commands.................................................................................. 311
Defining models..................................................................................................................... 312
What the model definition means ............................................................................ 312
Supplying an external file of BIPs ......................................................................................... 313
Defining phase descriptors and key components ................................................................... 314
Index 317
x  Contents User Guide for Multiflash for Windows

Overview
Introduction
Multiflash is a powerful and versatile system for modelling physical properties
and phase equilibria. It can be used as a stand-alone program or in conjunction
with other software. This manual describes the features of the Multiflash
Windows Graphical User Interface (GUI) and explains how it can be used to
solve engineering problems.
The Multiflash GUI

The Multiflash Windows GUI gives you access to the full capabilities of the
program, including:
 All the thermodynamic and transport properties needed for
engineering studies.
 Comprehensive fluid characterisation and model tuning for
petroleum fluids.
 Flash calculations to determine the phases present at specified
conditions and their type, composition and amounts.
 Modelling solids formation, including pure solids, halide scales,
hydrates, waxes and asphaltenes.
It is easy to set up all aspects of a study: components, models, units, type of
calculation etc. via menu options or tool bar buttons. This configuration can then
be saved for future use with the GUI or other applications.
Virtually any flash calculation can be carried out irrespective of the number and
type of phases present. Complete phase envelopes can be plotted showing phase
boundaries and critical points.
Multiflash Software System

In addition to the Windows GUI, it is possible to use the Multiflash calculation
engine in a variety of ways. There is a Multiflash add-in for Microsoft Excel and
an interface for use with Matlab. A CAPE-OPEN physical property package
interface allows Multiflash to be used by any application that is CAPE-OPEN
enabled. Multiflash may also be used with any software that can call a Windows
DLL. We provide support for applications written in various programming
languages including C++, Visual Basic and Fortran. Linux applications can also
be supported.
User Guide for Multiflash for Windows Overview  1

Separate documentation is available for each of these interfaces.
Document Organisation
The rest of this document is divided into the following sections.
New Features and Changes in Version 4.4 and

4.3
New developments and additions are listed, although more details of how to use
new features will be covered in the appropriate section. Information is also given
on changes to models or data which may give rise to different results from those
obtained with earlier versions of Multiflash. Version 4.3 was an interim internal
release of Multiflash.
New Features and Changes in Version 4.2

The developments done in the previous version are listed for reference.
Running Multiflash
Each section provides details on different aspects of the software.
Getting Started
Describes the different parts of the Multiflash main window and shows how to
use the program by running a simple example with step-by-step instructions.
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. Detailed specification of
the models can be found in a separate manual.
Components
The types 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.
Petroleum Fluids
Covers a number of topics related to modelling petroleum fluids: how to use the
information measured by a PVT laboratory to produce a compositional fluid
model; how to define the properties of petroleum fractions (pseudocomponents);
how to use experimental data to tune the petroleum fluid model.
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.
2  Overview User Guide for Multiflash for Windows

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

The Multiflash command language is used to store information about the
problem setup (databanks, components, models etc.) in Multiflash .mfl files.
Although users should not need to understand the command language it is fully
described in the Multiflash Command Reference manual.
In some circumstances it may be necessary to use Multiflash commands to
configure the software. The Tools menu has a Command option which allows
commands to be entered. Those commands that users of the Multiflash GUI may
find useful are discussed in the appropriate sections of the User Guide or in the
Appendix.
Installation
Information on how to install Multiflash software is provided in the separate
Installation Guide for Multiflash for Windows.
User Guide for Multiflash for Windows Overview  3

New Features and Changes in
Version 4.4 and 4.3
Introduction
As usual the new version includes the results of general maintenance and
improvements in numerical methods over the past year, as well as performance
enhancements. Specific features are described below.
Models
Descriptions and references detailing the models are provided in the User Guide
for Models and Physical Properties.
Huron-Vidal-Pedersen mixing rule

This mixing rule has been implemented for both the Peng-Robinson and the
Redlich-Kwong-Soave equations of state. Binary interaction parameters are
included for defined components.
Sutton Model for surface tension.

This model has been implemented to allow for a computationally inexpensive way to calculating the surface tension
of systems containing water.
LBC
It is now possible to specify a critical volume specifically for the LBC model for
each component, and to specify the LBC model parameters A1-A5.
Salt component
The salt pseudo-component can now be used with the following models: PR,
PRA, PRA-Infochem, PR78, PR78A, PR78A-Infochem, RKSA, and RKSA-
Infochem.
User Guide for Multiflash for Windows New Features and Changes in Version 4.4 and 4.3  5
High accuracy reference eos for water-ammonia
binary system
The Tiller-Roth high accuracy corresponding equation of state model for water-
ammonia binary system is now available.
New high accuracy reference eos

High accuracy reference eos for dodecane, DME, R161, R236EA and R236FA
are implemented in Multiflash 4.4. For the details, refer to “Multi-reference fluid
corresponding states (CSMA) model” on page 35.
Activity Coefficient models

For very light components, like N2, O2, etc, the Poynting is disabled. This
allows a more correct description of mixtures of these components with heavier
ones such as water.
Performance enhancements
The cubic equations of state and the CPA equations have been optimized in such
a way that from Multiflash 4.3 onwards it is possible to perform flash
calculations about 1.5 to 2 times faster than the previous versions of Multiflash.
Phase key components

It is now possible to specify multiple key components for phases. It is useful for
defining aqueous phases where the amount of water may be small.
Windows GUI
PVTSim import tool

It is now possible to import characterised fluids from PVTSim if they were
exported to a CHC file. This tool accepts systems with aqueous components, and
allows the user to define the desired number of phases. It is possible to select an
option to define models where the density of the gas phase is calculated using the
GERG-2008 model while the rest of the thermodynamic properties are calculated
using cubic models.
Models tab
The "Select Model Set" tab for Cubic Eos now also has an option where the
GERG 2008 model can be used to estimate the density of the vapour phase.
The Huron-Vidal-Pedersen mixing rule can be selected for PRA and RKSA.
A second liquid hydrocarbon was added to the Mercury model tab.
Inhibitor calculator
The salt component is again part of the inhibitor calculator.
6  New Features and Changes in Version 4.4 and 4.3 User Guide for Multiflash for Windows
Surface tension
The user can select the MacLeod-Sugden 2 phase variant for the calculation of
surface tension. This model can be selected under the MCSA (MCS-Advanced)
tab.
Petroleum Fraction Input Table

The user can now specify the critical volume to use in the LBC model in the
pseudo component generation table. The property has the name VCLBC and is
only used in the LBC model.
The maximum dimension of the petroleum fraction input table is now extended
from 25 to 100.
Tables
OLGA tables
The OLGA table generator was made more robust and more compliant with the
file format accepted by OLGA.
The maximum dimension of the temperature and pressure grid is now extended
from 50 to 100 for the current version of Multiflash.
Interfaces
Excel Interface
The Excel-AddIn can now be used in 64 bit versions of Microsoft Office 2010
and later.
CAPE-OPEN
Better support for multithreaded applications. Native support for 64bit
applications.
Databanks
Infodata
Saturated liquid surface tension of MEG, TEG corrected.
DIPPR
The DIPPR 2013 databank is now available on request.
User Guide for Multiflash for Windows New Features and Changes in Version 4.4 and 4.3  7
New Features and Changes in
Version 4.2
Introduction
As usual the new version includes the results of general maintenance and
improvements in numerical methods over the past year. Specific features are
described below.
Models
Descriptions and references detailing the models are provided in the User Guide
for Models and Physical Properties.
CSMA model
New high accuracy corresponding state models are implemented for the
refrigerants: R1234YF and R1234ZE(E) in Multiflash 4.2.
Mercury
The mercury model has been extended, so that it can now be used in connection
with PR78A and CPA, as well as with RKSA.
Poynting correction
The Poynting correction has been modified to give zero correction to the
enthalpy and entropy at saturation pressure. The enthalpy, entropy and heat
capacity calculated with activity coefficient models with Multiflash 4.2 are
therefore different from the results with previous version, but the new pure
component values are closer to correlations for saturated liquid Cp.
Activity coefficient model for gas phase

A new model, ACG (activity coefficient model for gas phase), has been included
in Multiflash to allow the user to calculate thermal properties for the gas phase
based on correlations for saturated liquid heat capacity and heat of vaporisation.
User Guide for Multiflash for Windows New Features and Changes in Version 4.2  9
LBC viscosity model
The LBC viscosity model has been fixed to work properly with petroleum
fraction with carbon number lower than C7.
Binary Interaction Parameters

Several BIPs were added or corrected in Multiflash version 4.2.
CPA model CPA

water/Hg, MEG/Hg, correct BIP for ethane/MEG, THF/water, O2+H2O, O2+n-octane
RKSA-Info, CPA and PR

H2 + (methane, ethane, propane, n-butane, n-pentane, n-hexane, n-heptane, n-
octane, n-decane, n-dodecane, n-hexadecane, n-eicosane, n-octacosane, n-
hexatriacontane, carbon dioxide and water)
RKSA
O2+H2O
PRA
O2+n-octane
Multiflash phase equilibrium algorithm

Make the Pressure-Enthalpy and Pressure-Entropy flashes more robust in
particular in the single phase region.
Flash calculations
In Multiflash 4.2, the Reid vapour pressure calculation is implemented. The Reid
vapour pressure (RVP) is usually employed by refineries to quantify and modify
the vaporization of gasolines and other volatile petroleum products. For the
details, see the section on “Reid Vapour Pressure” on page 162.
When the flash calculation involves solid phases, the errors about not being able
to calculate viscosity of a phase were removed. It is not possible to calculate
viscosity of solid phases.
The Joule-Thompson coefficient has been added as an output property of the
flash calculations.
Databanks
Infodata
New components, R365mfc, R1234YF and R-1234ZE(E) are added into the INFODATA databank.
The ideal gas heat capacities of Na+, Cl-, Ca++ and Br- in the databank have
been revised.
The ions Mg++, Ba++, Sr++, H+, CO3--, HCO3-, OH- and SO4—have been
added to the INFODATA databank.
10  New Features and Changes in Version 4.2 User Guide for Multiflash for Windows
Windows GUI
PVTSim import tool

It is now possible to import characterised fluids from PVTSim if they were
exported to a CHC file.
Reid vapour pressure

It is now possible to calculate the Reid Vapour pressure via the calculation
Liquid dropout and Wax precipitation curve

The liquid dropout and wax precipitation curve tools have been improved to
allow more control of the plotting.
New icon for Asphaltene precipitation curve

A new tool was added to determine graphically the precipitation of asphaltenes
at constant pressure.
Phase envelopes for solids

The automatic calculation of the V/L phase envelope as well as solid phase
boundaries has been made more robust.
It is now possible to right click in area of this plot and to a PT flash.
Hydrate models
The RKSA-Infochem model has been removed from the hydrate model selection
form, so that it is now only possible to select CPA-Infochem, with or without the
electrolyte model. It is possible to load an .mfl file with the RKSA-Infochem
hydrate model defined and use it in Multiflash 4.2.
Inhibitor calculator
The salt component tab has been removed from the inhibitor calculator.
PVT Analysis
The PVT analysis tool has been updated to allow the user to specify density in
API degrees.
Retrograde Dew Point

A new button was added to the main window to calculate automatically the
retrograde dew point at a fixed temperature with having to resort to the Fixed
Phase Fraction tool.
Calculation options
The calculations options have been simplified. Now only “Normal”, “Upper
Retrograde” and “Unspecified” are show for the type of solution where that is
necessary.
User Guide for Multiflash for Windows New Features and Changes in Version 4.2  11
Usability
In the forms where is necessary to input data, such as the Matching forms or the
PVT Analysis input, the user is warned that those values are lost if the dialog
box is closed without performing any operation with the data.
Tables
OLGA tables
The OLGA table generatas made more robust and more compliant with the file
format accepted by OLGA.
Multiflash Excel Interface
Joule-Thompson coefficient
The Joule Thompson coefficient was added to the list of properties that is
possible to get in a flash calculation.
12  New Features and Changes in Version 4.2 User Guide for Multiflash for Windows
Getting Started
Starting Multiflash
Start Multiflash by clicking on the Multiflash 4.4 shortcut on the desktop.
Alternatively, from the Windows Start menu choose All Programs and then
Multiflash 4. The Multiflash Main Window will be displayed.
Multiflash Main Window
User Guide for Multiflash for Windows Getting Started  13

Input section
The Input section of the Multiflash main window is located below the Toolbar. It
comprises the Conditions and Fluid identification widgets.
Conditions
The input conditions, such as temperature and pressure, used in Multiflash
calculations are shown below the Toolbar. The current units are shown next to
each value.
Fluid identification
A text box labelled Fluid identification is located to the right of the Conditions
section of the main window.
Use of the box is optional but it does allow you to add any comments or notes
and, subsequently, to save these as part of the .mfl file. This can be useful for
future reference, perhaps for identifying the study and the source of the fluid
data, etc. When the file is loaded again any notes will be shown in the Fluid
identification box.
Compositions
The Compositions button is located below the Fluid identification box. It allows
the fluid composition to be entered once components have been selected.
Results window
All the phase equilibrium flash calculations, error/warning messages, echoes and
results from Multiflash operations are displayed in the main window of
Multiflash.
Menu options
The menus allow you to control all aspects of running Multiflash. Options are
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 as
well as the saving and printing of results.
14  Getting Started User Guide for Multiflash for Windows

In menu items ending with triple dots you will need to define further items, such
as the directory and file to be loaded. A dialogue box will be displayed to allow
you to do this.
The last nine recently-used setup files are listed in the File menu. To load a file
from the list, double-click on the file name.
Edit
This controls the normal windows editing functions of Cut, Copy and Paste,
which can be used on text in the results window.
Select
The Select menu option allows you to select the fluid-phase components,
components that may appear as pure solids (Freeze-out Components), petroleum
fluid characterisation (PVT Lab. Input) physical property models, level of
property output, stream types, units of measurement and the use of starting
values for calculations. All the menu options except Use Starting Values activate
dialogue boxes which are described in later sections of this guide. Items marked
with the right pointing triangle contain submenus.

Tools
The Tools menu groups together options for displaying information about the
current problem, utilities for handling data and settings that control the
calculations or other aspects of the way Multiflash works.
The Command option can be used to enter Multiflash commands (see the
Appendix on page 311). This is not normally necessary but may sometimes be
useful for setting options that are not, otherwise, accessible in the Multiflash
GUI.
Pure Component Data and BIPs options allow you to view and edit the
properties of any component in the mixture and any binary interaction
parameters being used.
The Inhibitor calculator allows you to add water and hydrate inhibitors (alcohols,
glycols, salts) in volume, mass or molar units. A salt analysis may be entered in a
wider variety of units.
The Matching function tunes the properties of petroleum fractions in the mixture
to reproduce user-supplied measurements. The quantities for which data may be
supplied are: dew points, bubble points/GOR, liquid viscosity and liquid density.
The wax model may be tuned to match a wax appearance temperature or
precipitation data and the asphaltene model parameters may be tuned to match
flocculation or titration data.
The Blend Fluids option allows the user to blend (mix) a number of fluids by
mass, volume or molar amounts.
The Preferences option allows the user to set the default behaviour when
Multiflash is started. You can set the preferred units and the calculated
properties, the locations of files used by Multiflash, the appearance of the results
in the results window and the default models to be used for calculations. All

these preferences are stored in the Windows Registry. Any changed items will be
used the next time that Multiflash is started. Settings such as models and units
may be changed at any time during a Multiflash session using the Select menu
but this has no effect on the Preferences.
The Show option allows you to see the current problem status such as the whole
problem description or the models, pure component data source or BIP bank in
force.
Calculate
The Calculate menu provides a choice of flash calculations. Different types of
calculations are grouped together as: Standard Flashes; Bubble and Dew Point
Flashes; Fixed Phase Fraction Flashes; (see “Fixed phase fraction flashes” on
page 144), the tolerance calculation, (see “Tolerance calculations” on page 161),
the phase envelope calculation , (see “Phase Envelopes” on page 148) , phase
envelope for solids, special-purpose Hydrate and Wax calculations, liquid
dropout, waxes, asphaltene precipitation curve calculations, and Reid vapour
pressure calculation.
Table
The Table menu is for creating input files for use with other applications,
currently PIPESIM, OLGA and Prosper.
See “Interfaces with other programs” on page 183.
Help
The HELP menu enables you to get help on a variety of topics, see “Help” on
page 191.

The Toolbar
The Toolbar provides a quick way of accessing some of the most common
operations. Holding the cursor over a toolbar button displays a tool-tip that
describes its function. For example, the PT button for the flash at fixed P and T
calculation.
Defining a problem in Multiflash

This means selecting the components in the mixture and setting their
compositions, choosing the models you wish to use to calculate properties and
setting the input conditions (e.g. temperature and pressure). The steps are
described in detail in the appropriate sections below. In this tutorial we will first
use an existing problem file and then go through the steps required to set up a
problem from scratch.
Loading an existing problem file

Infochem supplies a series of sample problem setup files covering a variety of
typical problem types. These can be used as examples when testing the program
or can be used as a basis for defining your own setup files. By convention
problem setup files for Multiflash have the extension .mfl.
The file used for the simple tutorial is C4C5.mfl. 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.
Loading a problem setup file

The problem setup file for our tutorial is C4C5.mfl. To load the file:
1. From the File menu choose “Load Problem Setup”
Or
Click on the Load Problem Setup button on the toolbar.
This will display the file selection dialogue

which will show a list of available setup files (*.mfl) contained in the
problem files directory. By default this is the directory where Multiflash was
installed. This directory might be different if earlier versions of Multiflash
were used on your computer. After the Multiflash is launched, the
Multiflash working directory can be changed from the menu option,
Tools/Preferences/General/Folders.
2. Select C4C5.mfl and click on Open or double-click on the file name. The file
will be read by Multiflash and the contents are echoed in the Results
window. The file contains the complete definition of the problem including:
 Data sources
 Models
 Phases
 Components
 Compositions
 Temperature and pressure
The input conditions section of the main window will look like this
Calculations
You can now carry out a flash calculation at the specified temperature and
pressure by clicking on the PT flash toolbar button .
The results
The results of any calculations are displayed in the Results section of the main
Multiflash window.

You may need to scroll the window to see all the results. Size of window can
also be changed by clicking and dragging its borders and corners.
Additional calculations
Any of the input conditions may be changed by entering new values to overwrite
or supplement those shown in the Conditions 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 toolbar button or select the
calculation from the Calculate menu.
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” on page 69.
Some simple changes are shown below:
Change the pressure

1. Click in the Pressure box of the Conditions panel in the main
window and change the pressure to 14e5 Pa.
2. Click on P,T flash toolbar button
or
use the Calculate menu and choose Standard Flashes and then P.,T
Flash.
3. The calculation shows that the system is a one-phase liquid under
these conditions.
Change the composition

1. Click on the Compositions… button in the Fluid identification
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 “mole”
column of the drop-down table so that there are 9 moles of butane
and 1 mole of pentane.

2. Recalculate the P,T flash as above. The mixture is now two-phase.
Carry out an isenthalpic flash

1. Enter a value of 1000 in the Enthalpy box.
2. Click on the P,H flash toolbar button or use the Calculate

menu.
Setting up a new problem

To set up a new problem you must enter the following information:
 Data sources
 Models
 Components
 Compositions
 Input conditions
Clearing previous problems

You can restore all settings in Multiflash to the state when the program was
started by selecting the “Clear Problem Setup” option from the File menu.
Defining the components

Choose the components for any problem by clicking on Components in the
Select menu. Alternatively you can click on the Select Components toolbar
button, . Either will display the Select Components Dialogue box.
The default data source is the Infochem fluids databank which is called Infodata.
If you have licensed the DIPPR databank this may be selected from the drop-
down list.
Components may be selected in a variety of ways e.g. by name, by scrolling
through a list or by searching for a formula or substring. The various methods
are fully described in “Selecting components” on page 66.

Choose the components needed for the problem, in this case butane and pentane
as follows:
1. Make sure the Name option button is selected.
2. Click in the box next to “Enter name” and type
butane
and then press the <Enter> key or click on the Add button.
BUTANE is transferred to the Components selected list. Do the
same for pentane.
3. Click on the Close button, this will return you to the Main
Window.
Defining the models

To define the models and phases to be used for the calculations choose Model set
from the Select menu.
Each tab of this window groups together similar types of model, e.g. cubic
equations of state, activity coefficient models and so on.
For general advice on which models to choose for a particular application and
more information about each model, see “What types of model are available?”
on page 29 or consult the “Models and Physical Properties” manual.
We will use the Peng-Robinson equation of state: click on PR. You can also
change the transport property models and the phases to consider but the default
set will usually be appropriate.
Click on the Define Model button. The following message should confirm that
the models have been successfully defined.

Click on OK and then Close the Select Model set dialogue to return to the main
window.
Set 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 Condition section of the main window.
Compositions
To enter the composition click on the Composition button. The drop-down table
shows the components in the left-hand column. The amount of each component
in the mixture is typed in the right-hand column. The default unit for amounts is
moles. Note that the amounts do not have to sum to 1 or 100 or any other value.
Click on the Compositions button and enter 0.4 for butane and 0.6 for pentane.
The composition table can be hidden by clicking on the up-arrow button
Pressure and temperature

Other input conditions will depend on the type of flash calculation to be carried
out, e.g. for an isothermal flash you must enter a pressure and a temperature in
the appropriate text boxes and in the units shown next to them. The units may be
changed as described in the section “Units” on page 169.
Type 9e5 in the Pressure box and 375 in the temperature box.
Carrying out the flash calculation

To carry out a flash calculation you either click on the appropriate flash button
on the toolbar or select the required flash from the Calculate menu.
The most commonly encountered flash options have been allocated toolbar
buttons; these are the isothermal flash, dew and bubble points, isenthalpic and
isentropic flashes at fixed pressure and fixed phase fraction flashes.
Other flashes, such as isochoric flashes or isentropic and isenthalpic flashes at
fixed temperature, are specified using the Calculate menu. To calculate the
bubble point at the pressure of 9 bar click on
To carry out an isothermal flash at 9 bar and 375K click on

A short description of the function of each toolbar button is displayed when the
cursor is placed over the button.

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.
Compositions for a mixture may be altered as described above.
Ensure that all necessary input conditions are defined for the flash calculation
you wish to carry out and then click on the appropriate toolbar button or select
the required flash from the Calculate menu.
To replace a component or to add new components see “Adding, inserting,
replacing and deleting components” on page 69.
Phase envelope
You can plot the complete phase envelope by clicking on the phase envelope
button or selecting Phase Envelope from the Calculate menu.
Click on the VLE AutopPlot button; the vapour-liquid phase boundary will be
displayed in a separate window. Click No in response to the message "Maximum
number of points reached …" if the phase envelope is completed. If more points
along the phase envelope are required, click Yes to complete the envelope.

The legend can be changed by clicking Options button on the Phase Diagram
form.
The phase diagram may be edited or printed as described in, ”Customising the
phase envelope plot” on page 155. Alternatively it can be exported to Excel
(Excel 97 or later).
Saving the problem setup

Once you have defined the components and models you can create a problem
setup file containing this information for future use. If compositions and other
input conditions are set these values will also be saved in the file.
To save the setup either click on Save problem setup button, , or

select “Save Problem Setup” or” Save problem Setup As” from the File menu.
The dialogue box allows you to specify the name of the .mfl file and the
directory where you want it stored.

If the problem file to be saved is based on an existing file, the default file name
given will be the same as the existing one and a warning message will pop up.
Otherwise Multiflash will provide a default file name which can be overwritten.
Keep in mind that in order to write files into the default mfl directory you should
have a right to do this. If your system administrator deprived you of such a right,
it might be useful to copy the entire directory to somewhere in your working
space and continue to work with Multiflash in there.
Backup file
For any existing MFL files loaded to Multiflash, a backup file with a file
extension .MFB will be created if the existing MFL file is overwritten with the
changes.
Loading a existing MFL file

A warning message is given when loading a saved MFL file to Multiflash to
overwrite the current project.
Warning option for matching and PVT form

A warning message is given when leaving the form without matching the data
from all the matching forms and PVT forms.
Printing the output

You can print the output from your calculations by selecting “Print Results”
from the File menu or clicking on the Print Results button,
This Print dialogue (see below) allows you to select the printer and its settings
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 173. All the output from any Multiflash session is automatically stored in a
file called MFLASH.LOG in the Multiflash working directory. This file will be
re-named the next time the program is started. The names are allocated
sequentially as MFLASH_1.LOG, MFLASH_2.LOG, etc., up to
MFLASH_9.LOG.
If you wish to save the output to another file, select Save Results from the File
menu.
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 300kb of text. If there is too much output only the last 300kb is
displayed on the screen or in the log file.
How to exit the program

To exit Multiflash select Exit from the File menu. If the current fluid definition
has changed the user is asked if saving is necessary.

Technical support
For contact information see “Technical support” on page 194.

Models
Introduction
This section defines what a model is in terms of the Multiflash nomenclature,
which models are available and when you might wish to use them, as well as
how to specify and use them in Multiflash. For information on specifying
models, see “How to specify models in Multiflash” on page 47. Detailed model
descriptions may be found in our separate User Guide for Models and Physical
Properties.
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 depends on
pressure, temperature and composition.
What types of model are available?

The key calculation carried out in 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
where f i is the fugacity of component i in the vapour phase and f i l is the
fugacity of component i in the liquid phase.
The models used in Multiflash to represent the fugacities in terms of
temperature, pressure (and composition) 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 (EOS) method all thermodynamic 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 a combination of models
which include a representation of the excess properties.
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 component freezes or may be a particular solid phase such as a
hydrate, wax or asphaltene. Models used to represent these solids are discussed
below.
User Guide for Multiflash for Windows Models  29

The transport properties of a phase (viscosity, thermal conductivity and surface
tension) are generally derived from semi-empirical models which will be
discussed later.
Equation of state models

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 well-represent highly non-ideal chemical systems such as alcohol-
water. 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 parameters that 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
pure component 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 (PR) equation is a cubic equation of state.
30  Models User Guide for Multiflash for Windows

Peng-Robinson 1978 (PR78) equation of state
The 1978 revised version of the Peng-Robinson equation has a different
treatment for the parameter  . This model removes a defect in the original
equation where heavy components with higher acentric factors become more
volatile than components with somewhat lower acentric factors. For any mixture
containing components with acentric factors greater than 0.49 the PR78 equation
will give different results and must therefore be treated as a different model.
Redlich-Kwong (RK) and Redlich-Kwong-Soave

(RKS) equations
Like Peng-Robinson, the Redlich-Kwong and Redlich-Kwong-Soave equations
and their 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, PR78A 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. In Multiflash, 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. However, a third term is available, see
the User Guide for Models and Physical Properties, and the user may enter all
three coefficients as pure component properties.
Fitting the vapour pressure curve

For each component the equation of state a parameter is fitted by linear
regression to the vapour pressure over a range of reduced temperatures
corresponding to the stored data. Up to 5 coefficients may be used but fewer
coefficients will be fitted if there are insufficient data or if the extrapolation to
low temperatures is unrealistic. If there is no vapour pressure equation for a
component, the standard expression for each equation of state is used.
Mixing Rules
The standard mixing rule for the cubic equations of state is the, so-called, van
der Walls 1-fluid mixing rule. This is a simple recipe for obtaining the properties
of a mixture by combining the pure-component properties. It is a widely used
and highly effective method for many non-polar mixtures encountered in the oil
and gas industries.
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 User Guide for Models and
Physical Properties.

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,
PR78A) model sets which use the Peneloux correction, fit the EOS parameters to
match the vapour pressure and use the Van der Waals 1-fluid mixing rules.
RKSA with the Infochem mixing rules can be used as part of the hydrate model
and provides extra flexibility to represent the highly non-ideal aqueous system. It
does, however, require suitable BIPs for such systems.
The API variant of RKS is applicable to petroleum systems and mixtures
containing hydrogen. The RK EOS may be used instead of the ideal gas model
for the vapour phase of systems where the liquid phase is being modelled with an
activity coefficient model.
Finally, the GUI provides a checkbox that allows the user to use the GERG
2008 model to calculate the density of the vapour phase while estimating the rest
of the thermodynamic properties (e.g., fugacity coefficients, vapour pressures,
etc.) with the selected cubic Eos.
Cubic plus association (CPA) model

The CPA model consists of the Redlich-Kwong-Soave equation plus an
additional term based on Wertheim’s 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. The volume shift is a linear function of temperature which
is set to match the saturated liquid density at two different temperatures. For
light gases, a constant volume shift is used that is fitted to the gas’s liquid
density at a reduced temperature of 0.7.
When to use CPA.

The CPA model is the recommended model for hydrate calculations, or other
cases including water, methanol, ethanol, MEG, DEG, TEG and salts. For other
(non-polar) components CPA reduces to the RKSA EOS.
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 rule 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.
ZJ (Zudkevitch-Joffe) model
The ZJ equation of state model is a variant of the original RK cubic eos. Unlike
the original RK, the “a” and “b” parameters are expressed explicitly in terms of
the critical temperature and pressure, the “a” and “b” parameters in ZJ eos are
defined by simultaneously solving the equations of fugacity coefficients along
the saturation line and the equation of pressure for both vapour and liquid phase.
When to use ZJ model

The model provides a tool for giving better predictions on enthalpy departures of
saturated and compressed liquids, both pure and liquid mixtures with suitable
interaction parameters (BIPs). However the BIPs are required in order to use the
model as the default BIPs in our databank are not regressed against any
experimental data.
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 are 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 of an equation of state. The
mathematical structure is very complex and cannot be conveniently described in
this guide. Further information and references are provided in the User Guide for
Models and Physical Properties.
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. We also include the dipolar and quadrupolar terms when the dipole
moment and quadrupole moments are available.
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 pseudo components which must be set up as user-
defined components.
Using PC-SAFT, every pseudo component for a given polymer must be assigned
the same values of the pure-compound parameters SAFTSIGMA (in metres, not
Ångstrom 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 pseudo component knowing the molecular
weight. For polystyrene, for example, Gross and Sadowski give the ratio as
0.019, so for a polystyrene pseudo component of molecular weight 100000, the
SAFTM parameter should be set to 1000000.019=1900, etc.
Additionally, the user can define association parameters if the polymer forms
hydrogen bonds. These parameters are SAFTBETA which defines the
volumetric or entropic parameter, and SAFTEPSILON, the energy or enthalpy
parameter. Multiflash also provides an extension to the PC-SAFT definition: so
that the user can also supply a heat capacity parameter SAFTGAMMA for the
association term. For the association term to be non-zero, the user must also

define the parameter SAFTFF which denotes the number of donor bonding sites
per segment of polymer.
Values of PC-SAFT parameters for polymers can be found in Modelling
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 Modelling of polymer phase
equilibria using Perturbed-Chain SAFT by Tumakaka, Gross and Sadowski in
Fluid Phase Equilibria, 194-197, 541, (2002).
Multiflash allows the user to define up to four polymer segments which can be
used to define any number of homopolymers or copolymers following the
method of Tumakaka, Gross and Sadowski described in the reference above. If
the polymer is formed from only one type of segment, it is a homopolymer of
that segment; if it is formed of two or more types of segment, it is a copolymer.
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.
Lee-Kesler (LK) and Lee-Kesler-Plöcker (LKP)

equations of state
The LK and LKP methods are 3 parameter corresponding states methods based
on interpolating the reduced properties of a mixture between those of two
reference substances.
When to use LK or LKP

The methods predict fugacity coefficients, thermal properties and volumetric properties of a mixture. However, they
are rather slow and complex compared to the cubic equations of state and are not
particularly recommended for phase equilibrium calculations, although they can
yield accurate predictions for density and enthalpy. They 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 method is an 11 parameter non-cubic equation of state. For methane, ethane,
ethylene, propane, propylene, iso-butane, n-butane, iso-pentane, 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 is included for the convenience of users that wish to
reproduce calculations based on this method. It is not generally recommended.
The BWRS equation can give 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 we do not provide many BIPs in our databank. Owing to its complexity, it
requires more computing time than the cubic equations of state.

Multi-reference fluid corresponding states
(CSMA) model
The CSMA model is based on a collection of very accurate equations of state for
a number of reference fluids. It will provide accurate values of thermodynamic
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 following substances are included in the model:
acetone fluorine n-pentane R13
ammonia helium propane R134A
argon heptane propylene R14
sulphur
benzene cyclohexane dioxide R141B
iso-butane iso-hexane SF6 R142B
n-butane n-hexane toluene R143A
1-butene hydrogen water R152A
iso-butene hydrogen sulphide xenon R161
cis-2-butene krypton R11 R218
trans-2-butene methane R113 R22
carbon dioxide methanol R114 R227EA
carbon monoxide neon R115 R23
carbonyl sulphide nitrogen R116 R236EA
decane nitrogen trifluoride R12 R236FA
DME nonane R123 R245FA
dodecane octane R1234YF R32
ethane oxygen R1234ZE R365MFC
ethanol iso-pentane R124 R41
ethylene neo-pentane R125 RC318
The equations of state are taken from various sources and do not all have the
same quality or range of applicability.
Other hydrocarbons and petroleum fractions are included using a generalised
equation of state.
IAPWS-95
The reference equation of state used for water is the IAPWS-95 scientific
formulation. It is also available as a separate model option. For water the
recommended equations for transport properties have also been implemented.
Water-Ammonia
The high accuracy corresponding state model for water-ammonia binary system
is based on the work developed by Beiner Tillner-Roth and Daniel G . Friend.
The model not only has the high accuracy models for pure water and ammonia
but also has terms for correcting the mixing behaviour. The model covers the
thermodynamic space between the solid-liquid-vapour boundary and the critical
locus, and is also valid in the vapour and liquid phases for pressures up to 40
MPa. It represents vapour-liquid equilibrium properties with an uncertainty of
 0.01 in liquid and vapour mole fractions. Typical uncertainties in the single-
phase regions are  0.3% for the density and  200 J / mol for enthalpies.

Reference: Beiner Tillner-Roth and Daniel G . Friend, J. Phys. Chem. Ref.
Data,Vol, 27, No. 1, 1998.
Carbon Dioxide high-accuracy model

The reference EOS of Span & Wagner and high-accuracy models for the
transport properties of carbon dioxide are available as a separate model option.
GERG-2008
The CSMA model also includes the GERG-2004/2008 natural gas model. This is
an industry-standard high-accuracy model for mixtures of natural gas
components:
methane n-pentane argon
nitrogen iso-pentane oxygen
CO2 hexane hydrogen
ethane heptane CO2
propane octane water
n-butane nonane helium
iso-butane decane H2S
The model includes appropriate BIPs for all components in the list.
The model is fully described in the publication:, O. Kunz, R. Klimeck, W.
Wagner, M. Jaeschke, The GERG-2004 wide-range equation of state for natural
gases and other mixtures, GERG Technical Monograph 15 (2007).
Applicability
Applications of the model include: acid gas injection; natural gas pipelines and
processes; CO2 transport and carbon sequestration; water/steam systems; air;
instrument calibration and multi-phase meters.
The model performs best for mixtures that do not involve strong specific
interactions and for any of the pure substances in the list above. For mixtures,
appropriate binary interaction parameters are needed for good accuracy. BIPs are
included for the following components: CO2, H2S, methane, ethane, propane,
butane, pentane, and water. The mixture model is applicable to systems that do
not contain free water.
The GERG-2004/2008 model is a well-verified standard. It is probably the best
model for natural gas mixtures containing the components listed above.
GERG-2008 (Infochem extension)

GERG-2008 has been extended to provide a pseudo reference eos for petroleum
fractions or components that the high accuracy eos are not available. With this
extension, the model can be used for modelling the fluid phase behaviour of light
condensates containing small amounts of residuals or a mixture with some
components that the high accuracy eos are not available.
For a component or a peseudo-component in a mixture with no high accuracy
eos, a four-parameter corresponding-states principle (CSP) model proposed by
Sun and Ely(2005) is used to generalize the universal technical Equation of State
(EOS). This CSP model implemented in Multiflash is in the form of the
Helmholtz free energy, and two non-spherical fluids of propane and octane are
used as the reference fluids for nonpolar or weakly polar components. For the
details of the method, refer to the publication given below.

Reference: L. Sun, J.F. Ely, A corresponding states model for generalized
engineering equations of state, International Journal of Thermophysics, Vol. 26,
No. 3 (2005).
Activity coefficient methods

Liquid activity methods are based on the following equation for the fugacity of
component i in the mixture
f i l  xi i f i*, l
In an ideal solution the liquid fugacity of each component is directly proportional
to the mole fraction of the component, ie. the activity coefficient  i is equal to 1
The ideal solution assumes that all molecules interact with the same
intermolecular potential. This assumption is reasonable for molecules of a
similar size and similar type. However, most real mixtures deviate significantly
from ideality and the activity coefficient is different from unity.
Activity coefficient equations in Multiflash

A number of activity coefficient equations are available in Multiflash. Details of
each model may be found in the User Guide for Models and Physical Properties.
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.
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 correction
term. The Multiflash expression reduces to the standard Flory-Huggins theory if
all interaction parameters are set to zero. 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 been applied to model polymer systems but it has
been to some extent superseded by other models such as PC-SAFT. However,
Flory-Huggins theory still offers the advantages of speed and simplicity.
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 model 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 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 "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 model any combination of polar
and non-polar compounds including those exhibiting very strong non-ideality. If
the gas phase model is ideal 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 such 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 then you need to supply interaction
parameters for the missing values which match the model specification given
above and which are in the correct units. The parameters in Infobips are in
standard SI units, Jmol-1, except for Wilson A where the BIPs are dimensionless.
The user can supply BIPs in other units provided these units are specified
correctly.
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 component 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.
Scaling and general freeze-out model

In its general form, the freeze-out model can be applied to any solid phase of
fixed composition, which must be defined. The model can for example be
applied to hydrated salts such as monoethylene glycol (MEG) monohydrate or to
crystalline mineral salts, i.e. scales. The model is available as part of the hydrates
module where it may be applied to halide scales.
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 thermodynamic models
and calculation techniques for modelling gas hydrates.
Hydrate model
The recommended hydrate model is based on the CPA equation of state for the
fluid phases plus the van der Waals and Platteeuw model for the hydrate phases.
The original Infochem model is also available. It is based on a modification of
the RKS equation of state (RKSAINFO) for the fluid phases. The two models
usually perform in a very similar way. The models also represent the inhibition

effects and partitioning between phases of the common hydrate inhibitors:
methanol, ethanol, MEG, DEG, TEG and salts.
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, xenon and THF.
 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 allowing 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 reliable 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 solubility 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 conditions (temperature or pressure)
corresponding to the experimental determination of the hydrate dissociation
point. This is equivalent to the conditions where the first very small quantity of
hydrate appears after a sufficiently long time: the thermodynamic formation
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 is capable of predicting this phenomenon, 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. We can provide alternative model parameters if it required to
change the behaviour of either model.
Nucleation model
The nucleation model was developed in collaboration with BP as part of the
EUCHARIS joint industry project. This model is an extension of the existing
thermodynamic model for hydrates described above. In order to extend the
nucleation model for use with Multiflash, 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.

Comparisons of model predictions with experimental data have been made
where possible. In general measurements of hydrate nucleation result in an
experimental error of  2ºC and predictions are usually within this error band.
With the combination of the hydrate model and the nucleation model it is
possible to predict the hydrate risk area which lies between the formation and
dissociation boundaries.
Inhibitor modelling
Thermodynamic hydrate inhibitors decrease the temperature or increase the
pressure at which hydrates will form from a given gas mixture.
The CPA-based hydrate model includes parameters for water with methanol,
ethanol, MEG, DEG, TEG and salts. The RKSAINFO-based model also includes
parameters for some less-common inhibitors: iso-propanol, propylene glycol and
glycerol.
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, ethanol, MEG, DEG and TEG. This
involves representing simultaneously hydrate dissociation
temperatures, depression of freezing point data and vapour-liquid
equilibrium data.
 An electrolyte model is available in Multiflash, and a salinity
calculator tool is provided (see “Salt calculator” on page 81) which
allows the salt composition to be entered in a variety of ways. The
Electrolyte model includes the ions: Na+, K+, Ca++, Cl- and Br-,
and the salinity calculator can be used to convert a water analysis
that includes other ions into an equivalent amount of Na+, K+,
Ca++ , Cl- and Br-, or salt pseudo-component.
 The solubility of hydrocarbons and light gases in water/inhibitor
mixtures has also been represented.
Modelling wax precipitation

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.
The wax model in Multiflash was developed by Coutinho. The main features of
the model are:
 It 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.
 It 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.
 It requires that the normal paraffins are explicitly present in the fluid
model, as these are the wax forming components. It is essential to use the
Infochem petroleum fluid characterisation procedure 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 option in the Multiflash
implementation is RKSA.
Modelling asphaltene flocculation

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 becomes more soluble 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 Multiflash asphaltene model is a variant of CPA, where the association term
is used 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 described by the van der Waals 1-fluid
mixing rule with the usual binary interaction parameters kij so the asphaltene
model is completely compatible with existing engineering approaches that work
well for describing vapour-liquid equilibria. The model is a computationally-
efficient way of incorporating complex chemical effects into a cubic equation of
state.
In the following publication the CPA based asphaltene model in Multiflash is
compared to a PC-SAFT approach from the literature: Zhang, X., Pedrosa, N.
and Moorwood, T., Modeling asphaltene phase behaviour: Comparison of
methods for flow assurance studies, Energy Fuels, 26 (5), 2011.
Other thermodynamic models

Multiflash also includes the COSTALD a corresponding states method for
estimating the density of liquid mixtures.
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 several 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
SuperTRAPP Model
The SuperTRAPP method is a predictive extended corresponding states model
that uses propane as a reference fluid. It can predict the viscosity of petroleum
fluids and well-defined components over the entire phase range from the dilute
gas to the dense fluid. The Infochem implementation of SuperTRAPP model
includes modification to ensure that the viscosity of aqueous solutions of
methanol, ethanol MEG, DEG and TEG or salts and ions are predicted
reasonably well. Overall the SuperTRAPP method is the most versatile method
for viscosity predictions and its performance is generally better than the other
methods available in Multiflash. We would recommend this method for oil and
gas application. It is the default viscosity model for use with equations of state.
Reference: Huber, M. L. & Hanley, H.J.M. (1996) The corresponding-states
principle: Dense Fluids. In J. Millat, J. H. Dymond & C. A. Nieto (Eds.),
Transport properties of Fluids: Their correlation, Prediction and Estimation.
Cambridge University Press.
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.
Reference: Pedersen, Fredenslund and Thomassen, Properties of Oils and
Natural Gases, Gulf Publishing Co., (1989).
Twu Model
This is a predictive model suitable for oils. It is based on a correlation of the API
monograph 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 model is 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 Lohrenz 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 SuperTRAPP 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
SuperTRAPP thermal conductivity method
The SuperTRAPP method is an extended corresponding states model that uses
propane as a reference fluid. It is applicable to both gas and liquid phases. The
model can be used for petroleum fluids and well-defined components. The
thermal conductivity is defined as the sum of internal and translational
contributions. The latter are divided into three contributions: dilute gas, residual
and critical enhancement. The Multiflash model does not include a critical
enhancement term. For pure substances this can result in under-prediction of the
thermal conductivity near the critical region. However for a mixture the critical
enhancement is usually very small and negligible. The performance of the Super
TRAPP method is generally better than the CLS method.
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
Linear Gradient Theory model
The Linear Gradient Theory model uses the properties of the phases in
equilibrium to determine the interfacial tension. The key property is the density
gradient that exists across the interface. With this model it is possible to estimate
the interfacial tension between Liquid/Gas and Liquid/Liquid phases. It can be
used in combination with the any EOS-based fluid model except: LKP, CSMA;
the asphaltene model.
Reference: Zuo, Y. X. and Stenby, E. H., A Linear Gradient Theory Model for
Calculating Interfacial Tensions of Mixtures, Journal of Colloid & Interface
Science, 182 p12, Elsevier (1996).
Macleod-Sugden method (MCS).

This method predicts the surface tension (liquid-vapour) of a 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. In this implementation the
vapour phase is described by the ideal gas equation.
Macleod-Sugden 2-phase variant (MCSA).

This method predicts the surface tension (liquid-vapour) of a 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. In this implementation the
gas phase is described by the selected model for the gas phase (instead of the
ideal gas equation) and therefore is more accurate than the 1-phase variant.
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 phase diffusion coefficients. It is an empirical
modification of Chapman-Enskog theory.
Hayduk-Minhas method
The Hayduk-Minhas method calculates liquid phase diffusion coefficients. It
consists of a number of empirical correlations for different classes of mixture.

How to specify models in Multiflash
Using the menu

From the Select menu choose Model Set. The models selection dialogue is
shown below.
Under each tab are listed similar types of models or models for different
applications. Unless you have already set other default model preferences (see
below) the Cubic EoS tab is displayed with RKSA as the default model. The
default transport property models are shown. Other models can be selected or the
transport property calculations can be turned off by selecting None. Diffusion
coefficient models can be added if required.
For most model choices up to four phases may be considered. These are: gas,
liquid1, liquid2 and water. You can 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 deselecting liquid2 and water may speed up
calculations and make the phase equilibrium easier to solve.
Once you are satisfied with your model selection click the Define Model button
and you will see a message to confirming your choice.
Click OK and then Close to return to the main Multiflash window.

Loading a model from a .mfl file
When you load an .mfl file that includes model definitions you do not need to go
through the Select Model Set process unless you wish to change details of the
models or phases. The options shown in the Select Model Set window reflect as
closely as possible the contents of the .mfl file loaded but it is possible to have
options in the file that do not correspond to options that can be displayed.
Setting up preferred models in Multiflash

If you wish to have Multiflash always start up with your preferred model
selection you can do this by selecting Preferences/Models from the Tools menu.
The options are as shown for Select/Model Set above. The preferred set of
models and phases is stored in the Windows Registry and will be in force the
next time you start Multiflash. You can still select any other models as required.
How to change a model

You may wish to compare the predictions from one model with those from
another. This is easily achieved. Selecting a new model set will remove all
existing model-related information including: thermodynamic models; transport
property model; phases and BIPs.
For example, all you need to do to change from using RKSA to Peng-Robinson:
open the Select Model Set dialogue from the Select menu and click on PR. This
action 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 current methods for calculating the transport
properties.
Models for solid phases
Hydrates
From the Select menu choose Model Set and then click on the Hydrates tab.

The fluid model used in conjunction with the solid phase hydrate model is CPA-
Infochem. The model includes parameters to describe the effect of
thermodynamic hydrate inhibitors on hydrate formation and the partitioning of
the inhibitor between aqueous, gas and oil phases. The inhibitors include:
methanol, ethanol, MEG, DEG and TEG.
To model the effect of salts it is necessary to select the “CPA-Infochem +
Electrolyte” model, which combines the electrolyte model in Multiflash with the
CPA-Infochem model. The model is described in the section “Inhibitor
modelling” on page 42.
The default setting is to include models for hydrate structures: 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 with high concentration of methane or H2S, where
the most stable hydrate structure can change from Hydrate 2 at low pressures to
Hydrate 1 at high pressures. Hydrate structure H is unlikely to be present in most
practical situations but may be selected if required.
Calculation of the hydrate dissociation temperature and pressure will be quicker
if you exclude the hydrate nucleation option. However, if you want to include
the nucleation model select Phase Nucleation from the list of phases.
With the electrolyte model it is possible to allow for the formation of Halide
scales. If this option is selected then the appropriate phases will be added
automatically, based on the component formula, e.g. NaCl, NaCl.2H2O, KCl,
CaCL2, CaCl2.2H2O, CaCl2.4H2O, CaCl2.6H2O, NaBr, NaBr.2H2O, KBR or
CaBr2.6H2O. The Halide Scales option will only be available if the Electrolyte
model is selected and will slow down calculations so should only be used if solid
formation is suspected.
Pure solid phase

The freeze-out model can be applied to describe any pure solid component such
as ice, CO2 etc. It may ne used in conjunction with any model set for the fluid
phases but most commonly will be used with one of the cubic EoS.
From the Select menu choose ‘Freeze-out Components’. This will produce a
window displaying the components in the stream, e.g.

Checking, or unchecking, the box next to each name allows you to add or
remove the freeze-out model for that component. Each solid component may
form a separate phase. There is a limit (20) on the total number of (fluid and
solid) phases that may be considered.
A message box will appear to confirm that the model has been defined (or
removed) for the selected compound, e.g.
The name assigned to each pure solid phase is “SOLID” plus the compound
name, e.g. ‘SOLIDEICOSANE’ (except in the case of water where it will be
ICE).
Waxes
The wax model in Multiflash is the Coutinho model, described in “Modelling
wax ” on page 42. To define the wax model select the Waxes tab. Fluid phases
are represented by the RKSA model.
For more information on how to use the wax model see “Case studies – Wax
precipitation” on page 260.

The default phases include water. This may be deselected if no water is present.
The transport property models apply to the fluid phases. Click on Define Model
and then Close.
Asphaltenes
To define the asphaltene model select the ‘Asphaltenes’ tab. Fluid phases are
represented by the RKSA model. Water is not one of the default phases but may
be added if required. Click on Define Model and then Close.
For more information on how to make best use of the asphaltene model see
“Case studies – Asphaltene flocculation” on page 267.

Combined Solids Model
The Combined Solids tab allows you to specify any combination of wax, hydrate
and asphaltene solid phases. The fluid phase model is RKSA-Infochem and the
effect of salts on hydrates is represented by the electrolyte model.
If you define only one type of solid you will be asked to use the individual solid
model tab.
Troubleshooting - models
Although each version of Multiflash is thoroughly tested it is always possible
that you may come across problems. Please report any errors to us so that they
can be investigated and corrected.
There are other problems related to using Multiflash that can be resolved by the
user. Some of those related to models are discussed below; others will be
outlined in the relevant section.
Model is not available

If a model on a Select Model Set tab is greyed out this usually means that it is an optional add-on and has not been
licensed. You may not have licensed all the possible model options. The optional
models include: hydrates; wax; asphaltenes; mercury; PC-SAFT; CSMA;
IAPWS-95 and the CO2 High Accuracy model.
Groups not available for UNIFAC model

The UNIFAC model generates the binary interaction parameters 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. Complex cyclic components are typical examples. If this is
the case then you will see a warning message

and in the main window
*** WARNING -13201 ***
Missing UNIFAC structure for one or more components
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 standard 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 is defined with a separate gas phase model and
isothermal flashes will apparently work with the stream being reported as all gas.
It is possible to add user-defined UNIFAC groups, although there are no specific
menu options. You would have to enter commands through the command box.
Information on the commands can be found in the Multiflash Command
Reference Manual.
Binary interaction parameters

Binary interaction parameters (BIPs) are adjustable factors that 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. For the UNIFAC and PSRK models, BIPs are
predicted by group contribution methods and 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.
BIPs and models

The more a BIP varies from its default value, the greater the adjustment required
to make the underlying model fit measured data. For some models the BIPs have
some physical significance but they are usually treated as empirical adjustment
factors. Different models also require different numbers of BIPs.
The cubic equations of state (RK, RKS, RKSA, PR, PR78, PRA. PR78A, ZJ)
require only a single BIP that may be constant or linear or quadratic function of
temperature. The default value is zero. A BIP will usually have a small positive
or negative value and the magnitude is usually much less than 1. For LK, LKP
and CSMA the default value of the interaction parameter 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 RKSA-Infochem mixing rule or the Huron-Vidal-Pedersen (HVP) 3
BIPs are needed.
It is important to note that the HVP mixing rule can work with two different
types of BIP sets. For information on how to indicate which BIP set is being
used, please refer to the User Guide for Models and Physical Properties.
PC-SAFT requires two symmetric BIPs, in addition to the pure component
model parameters. The default value for both is zero.
CPA uses the same interaction parameters as RKSA with the addition of three
association parameters to describe cross association and self association where
this occurs.
Activity models generally reduce to the ideal mixing model when all BIPs are
zero (the default value). 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 a single symmetric
BIP with a default value of zero.
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 banks are applicable to oil and gas processing operations and
called appropriately, OILANDGAS and INFOBIPS.
INFOBIPS contains all the BIPs for the cubic equation of state models PR, PRA,
PR78, PR78A, PRA-HVP, RKS, RKSA, RKSA-HVP, RKSA (Infochem) and
CPA for hydrocarbons, water, methanol, glycols, H2S, CO2 and N2. It also
includes BIPS for WilsonE and the VLE variants of NRTL and UNIQUAC,
based on the data reported in the Dechema Chemistry Data Series. Other BIPs
are also included for models such as CSMA, GERG-2008, BWRS and LKP.
These values are generally for particular mixtures not covered in the standard
correlations.
OILANDGAS contains BIP correlations that can be used to estimate BIPs for the
PR, PR78, RKS, CPA and LKP models for hydrocarbon and light gas mixtures
that include petroleum fractions.
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 the DIPPR databank that 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. When an equation
of state model is defined Multiflash will first search INFOBIPS and then
OILANDGAS. If any BIPs 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.
Viewing BIP values

You can look at the values of any BIPs used in Multiflash calculations, including
those from the INFOBIPS databank and any supplied by the user. To do this
Define your model and mixture or load a problem setup file.
From the Tools menu select BIPs. The Show BIP Values window will be
displayed. The following example shows BIPs for decane and water for the RKS
model.
A BIP dataset is assigned when the model is defined. The number of BIP
datasets listed depends on the models that use BIPs and the number of BIPs for
the model (see below). In the above example RKSBIP identifies the BIPs for the
RKS EoS and LGSTBIP identifies the BIPs for the LG surface tension model.
Select the RKSBIP dataset and click on Edit to view or change BIP values or the
temperature dependence of the BIPs.
The Write to Output button displays the information in the results window:
show bipset RKSBIP;
BIPSET: RKSBIP
COMPS ORDER VALUES
1 2 0 0.5055762
TEMPERATURE FUNCTION: EOS UNITS: none
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, PR78BIP,
PR78ABIP, RKSABIP, RKSABIP3 (for RKSA + Infochem mixing rule ),
LKBIP, LKPBIP, WILSONBIP2, NRTLBIP3, UNIQUACBIP2 for VLE

versions of the model, NRTLLLEBIP3, UNIQUACLLEBIP2 for the LLE
implementations. 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. Regular Solution and Flory
Huggins BIPs are named REGULARBIP.
The components are referred to by the number they are assigned in Multiflash,
i.e. the sequence in which they appear 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 T-dependence and 2
that it has quadratic T-dependence.
The final line shows you the name of the temperature function. This will be EOS
for equations of state or a dimensionless BIP, such as REGULARBIP for Flory
Huggins or Regular Solution. Activity models are assigned an Activity
temperature function, while the first set of CPA or PC-SAFT BIPs (ASSOCBIP,
SAFTBIP) will be labelled EOS and the second (ASSOCBIP-2, SAFTBIP-2)
will be labelled Association. Multiflash will check that the correct temperature
function is used for the model selected. For equations of state (EOS) the function
is,
kij  a0  a1T  a2T 2

For the association term, the first BIP adjusts the volume parameter, the second
the energy parameter and the third the heat capacity parameter.
The final element is the Unit for the BIP. See below for more information.
A second example shows output for the methanol plus water binary and the
RKSA (Infochem) model. 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
a linear temperature dependence.
In a third example we consider a mixture of water, methanol, methane, and
ethane, and the RKS-HVP model. The HVP mixing rule can work with two
different types of BIPs, 1) "VDW-like" parameters (i.e., kij), which are
symmetrical, dimensionless, and are equal to those used in the classical mixing
rule of the RKS equation. 2) "HVP-like" parameters, which are composed of
symmetrical (ij) and asymmetrical (gij/R) BIPs, and where the asymmetrical
parameters have units of K.

We show below the output obtained for this mixture and model. In this case all
pairs except one have “HVP-like” BIPs defined. Only the pair methane-ethane
has “VDW-like” parameters, indicated by the absence of a symmetric BIP for
this pair.
If the user has access to additional "HVP-like" parameters to those in Multiflash,

these can be easily introduced by directly writing them in the output window.
In the case of the asymmetrical parameters, care must be taken of introducing
them in the correct order. For example, if the BIP found in the literature indicates
that it corresponds to water-methanol it should be entered in the cell
corresponding to the row "water" and column "methanol" (i.e., in the example
above, the upper diagonal value of 276).
Units for BIPs

The BIPs for most equation of state methods, Wilson A, Regular Solution and
Flory Huggins are dimensionless. For other activity methods and the two CPA
association parameters the BIPs have associated units. The default units in
Multiflash are J/mole. If BIPs from external sources are used in Multiflash it is
important that either the BIP units are changed to match the input values or the
numeric values of the BIPs are changed to J/mole.
The choice of units appears once the Units button is activated in the BIP display.

J/mol is the Multiflash standard for the dimensioned activity model BIPs.
cal/mol and K are the values used in the Dechema Data Series for activity model
VLE and LLE BIPs. The “Aspen” format allows you to transfer the BIP values
for the NRTL equation from Aspen Plus without further change.
The actual input functions for the activity BIPs are as follows:
In J/mol K Aij=a + bT + cT2
In cal/mol K Aij/4.184=a + bT + cT2
In K Aij/R=a + bT + cT2
Dimensionless Aij/RT=a + b/T + cT
Aspen format Aij/RT=a + b/T + cT
For the NRTL equation, the  parameter is defined as follows:
All formats except Aspen ij= a + bT + cT2
Aspen format ij= a + b(T-273.15) + c(T-273.15)2
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, that you have specified
and supplied BIPs in the correct units and in the correct order.
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 the expected
value. 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 9 bar has changed from 371K to 359K.

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.
If the model is changed the user-supplied BIPs values will be retained unless a
model is selected that does not use the same BIP dataset. For example, if you
simply want to change the number of phases or use a different transport property
model, you don’t have to enter your user BIPs again.
You can save your new BIPs for the current case permanently 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 should define the model and components and
then use the BIPSet window to enter the values and then save the file.
If the units of the BIPs you want to enter are different from the default units in
Multiflash you can change the units as described above before entering the
values. If you change the units after entering the BIP values or for existing BIPs
in Multiflash, the values will automatically be updated.
If you have a file of BIPs that contains values for components that are not in
your current stream you will see a warning message for each missing pair:
*** WARNING -223 ***
One or more components in this BIP set are not
currently defined
If you know the reason for the warning it may be ignored because BIPs for
components that are in the stream will be loaded and included in any subsequent
calculations.
You should note that if you change the model such that a different BIPset is
required then the BIPs read from a file will be discarded and replaced by those
from databanks or correlations included in the new definition.
BIPs for CSMA and GERG mixing rule

For the CSMA with GERG mixing rule or GERG-2008 models, three BIPs are
required for improving the critical temperature and volume of the mixture as
well as the weighting factor for the binary high accuracy departure functions for
modelling the mixing behaviour. The default names for the three BIPs with the
GERG-2008 model are GERGBIP, GERGBIP-2 and GERGBIP-3. For
GERGBIP and GERGBIP-2 each pair of components can potentially have three
parameter coefficients. The first two are for the constant or linear (in
temperature) interaction parameter. These two are symmetric. However the third
value (0.9963365 and 1.003677 in the table for GERGBIP for methane and
ethane as shown below) is actually a reciprocal of each other. So when entering
this value, you need to be careful about the order of the BIP.
The third BIP, GERGBIP-3 is the weighting factor of the binary high accuracy
departure functions. By default, it is set to zero. If the mixing rule has the
departure function equation available for the binary system, a non-zero value
will be displayed otherwise it will be zero.

Troubleshooting - BIPs
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 Chemistry Data
ISSN 0840-9645 Series which is in several volumes. It is useful to note that their standard
Volume I to XVI convention is to report activity model BIPs for VLE in cal/mol. Either these
Publisher: Dechema need to be converted to J/mol for use in Multiflash or the Units for BIPs must be
changed to cal/mol. Similarly, the LLE BIPs for UNIQUAC and NRTL either
need to be multiplied by the gas constant R (8.314 JK-1mol-1) for use in
Multiflash or the BIP units must be set to K.
BIP databank
The names of the main BIP databanks for equations of state and activity
coefficient models are INFOBIPS and OILANDGAS, which are the names
included automatically in all the relevant model sets. From Multiflash 4.2, the
BIPs for all the relevant model sets are defined from INFOBIPS and BIPs
correlations are obtained from OILANDGAS.
Differences between the PR Model in Multiflash and

Aspen Hysys
The Peng-Robinson (PR) and PR78 equation of state (EOS) models implemented
in Multiflash is based on the original publications by Peng and Robinson (1976,
1978). By default the PR model is used for all phase properties: fugacities,
density and thermal properties.
Based on information in Aspen Hysys documentation the standard Hysys PR
model works as follows. The fugacity coefficients of components in a mixture
are obtained from the PR78 EOS. This means that if the components in
Multiflash have the same critical properties, acentric factors and BIPs as in
Hysys, the calculated phase equilibrium (phase amounts and compositions) at
given pressure and temperature should be very similar. However, the volumetric
properties (density) and thermal properties (enthalpy, entropy) may differ. The
reason for this is that the Hysys model uses a version of the COSTALD model to
obtain the liquid density at sub-critical conditions. Thermal properties are
evaluated from the Lee-Kesler model.
The recommended version of the PR model in Multiflash is PRA78A. Amongst
other features, this model allows the use of a volume-shift adjustment that
considerably improves density predictions compared to the original PR or PR78

models. To obtain a match between Hysys PR liquid densities and PRA78A for
systems including petroleum fractions it is recommended to use the volume
matching tool (see section “Matching density/volume”) to adjust the volume
shift parameters to match densities from Hysys. It is also possible to specify that
the LK model should be used in Multiflash to calculate thermal properties. You
should contact Infochem technical support for assistance if you wish to do this.
Note that absolute values of enthalpy and entropy in Multiflash and Hysys will,
most likely, differ irrespective of the model used. This is because the (arbitrary)
enthalpy and entropy zero points are different. Enthalpy and entropy differences
should, however, be comparable.

Components
Introduction
Multiflash recognises two 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 pseudo component, 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.
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 several hundred compounds and is
always supplied as part of Multiflash. DIPPR, produced under the auspices of
AIChE, currently has data for around 2000 compounds, and 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 66.
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
Standard Ideal Gas Enthalpy of
Formation at 298.15K
User Guide for Multiflash for Windows Components  63

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.
In addition there is a group of properties that allow unique identification of the
name and type of the component. These are
TYPE
CAS number
FORMULA
FAMILY code (Deprecated since DIPPR 2013)
Normal databank components will be TYPE 1, petroleum fractions will usually
be TYPE 12.
Temperature Dependent Properties
Solid Density
Liquid density
Vapour Pressure
Enthalpy change on evaporation (latent heat)
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.
The INFODATA databank also stores some additional properties which include:
Constant properties
Polarizability
Quadrupole moment
PC-SAFT model parameters
Entropy of Formation
Specific gravity
Isobaric expansivity
Temperature Dependent Properties
Relative permittivity (dielectric constant)
64  Components User Guide for Multiflash for Windows

These properties are available for a small proportion of components in the
databank.
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 reasonably beyond the temperature limits of
the stored correlation.
INFODATA contains only a limited range of components mainly suitable for oil
and gas applications. 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.
Petroleum fractions
Petroleum fractions are discussed in detail in the section “Petroleum Fluids”
Defining a mixture
In this section we describe how to define a mixture containing normal
components. To define a mixture including petroleum fractions or to set up fluid
characterisation based on a PVT laboratory report see “Petroleum fluids” on
page 89.
The maximum number of components in any mixture in the
current version of Multiflash is 200.
From the Select menu choose Components or click on the Select Components
toolbar button
This will display the Select Components dialogue box

Specifying the data source
The Infochem fluids databank is the default data source. To choose any of the
other data sources click on the button to the right of data source and select the
required data source from the list.
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 name

This is a simple and rapid method once you know the components available.
Click the Name option button.
You can enter the name of the component you wish to add to the mixture in the
Enter Name box; it may be in upper- or lower-case or any combination. Press
<Enter> or click the Add button..
If you make a spelling error or if the component is not in the selected data bank
you will get an error message
Select components by scrolling through a list

Choose the All Components option button and a list of the standard names
for the compounds stored in the chosen databank 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 names are not sorted; they appear in the order of
components in the databank selected.

The component may then be selected for use in Multiflash either by double-
clicking on the name or by clicking on the name to highlight the component and
then clicking the Add button. The name of the selected compound will then
appear in the “Components selected in Multiflash” box. Further components may
be selected in the same way.
Synonyms
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 alternative names (synonyms)
stored for that compound.
Click the Synonyms option button and type the name in the Enter name box.
Press <Enter> or click 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 choose 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 of synonyms for ‘glycol’ shown above ‘ethylene glycol’ is the main
name for the component in the INFODATA databank but any of the alternatives
may be used. 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 Enter
formula 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. You m ay
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, for example,
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 new compound as usual by entering the name or highlighting it in a
list
Highlight (by clicking on it) the compound in the Compounds selected list above
which you wish to insert the new component
Click on the insert button.
Deleting components
If you wish to remove one or more components from the selected list then, in the
Compounds selected text box:
Select the component(s), then
Click on the Delete button
The compound(s) 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 197 . 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. For details of the correlations used see the User
Guide for Models and Physical Properties.
Any of these data may be overwritten by typing the new value in the appropriate
cell in the correct units. The units for the constant properties may be changed
using the Units button. Temperature-dependent property correlations always use
Kelvin as the unit of temperature. 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
You may add user-defined pure components, for instance when the component
you require is not available in our databanks. However, you should note that for
this option you must supply all the data required for the models you use. This
will include constants such as the critical properties and coefficients for the
temperature dependent correlations such as perfect gas Cp etc. The minimum
data requirements for different models are listed in “Models and input
requirements” on page 74. This option is not recommended for petroleum
fractions; see “Petroleum fluids” on page 89.
Adding a user-defined component

To add a new user-defined component open the Select Components dialog box
and select User-defined component from the Data source list. You should then
enter the component name and press <Enter> or click on Add. This operation
creates a new component with a name but no data.

Specifying data for a user-defined component
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 and select your user-defined component.
Constants
Click Edit to enter constant values.. The Value column will initially be empty.
Enter the property values for your component, e.g.
You can change the units if necessary. Not all properties must be given a value;
it depends on the models you use.
Temperature-dependent properties
To enter a temperature dependent property, such as the perfect gas heat capacity,
choose the property and click on Edit, or double click on the property
description. A form will be displayed showing 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 User Guide for
Models and Physical Properties, 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.
Models and input requirements

A basic minimum data set for any component should include the following:
 molecular weight,
 critical temperature,
 critical pressure,
 acentric factor
 perfect gas heat capacity.
The following table lists the data required in addition to the above for each
model.

Model Additional data required
Thermodynamic
RKS None
RKSAPI None
RKSA vapour pressure and saturated liquid density
RKSAINFO As RKSA
RKS-HVP None
PR, PR78 None
PR-HVP None
PRA, PR78A As RKSA
PSRK As RKSA plus UNIFAC subgroup structures
LK, LKP None
BWRS critical volume (VCRIT)
CSMA or GERG-2008 None
CPA As RKSA plus association parameters (ASSBE,
ASSEP, ASSGA) for associating components.
PC-SAFT PC-SAFT parameters (SAFTEK, SAFTSIGMA,
SAFTM, SAFTKAPPA, SAFTEPSILON,
SAFTFF
Note (1) critical properties and acentric factor are
used 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 mixing vapour pressure, saturated liquid density,
enthalpy of evaporation
NRTL As Ideal mixing
Wilson E As Ideal mixing
UNIQUAC As Ideal mixing plus UNIQUAC surface and
volume parameters (UNIQQ, UNIQR)
UNIFAC As Ideal mixing plus UNIFAC subgroup
structures (UNIFAC)
Dortmund Modified As Ideal mixing plus UNIFAC subgroup
UNIFAC structures (UNIFAC)
Regular Solution As Ideal mixing plus solubility parameter
(SOLUPAR) and molar volume at 25°C (V25).
Flory-Huggins As Ideal mixing plus solubility parameter
(SOLUPAR) and molar volume at 25°C (V25).
Perfect gas None
RK None
Hayden O’Connell radius of gyration (RADGYR), dipole moment
(DIPOLEMOMENT), Hayden-O’Connell
association parameter (HOCASS)
Pure solid 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 vapour pressure, saturated liquid density
Mercury partitioning As specified fluid model
model

Transport properties
Pedersen None
Twu boiling point (TBOIL), vapour pressure,
saturated liquid density
LBC critical volume (VCRIT), or model specific VC
Lohrenz-Bray-Clarke (VCLBC), specific gravity (SG), dipole moment
(DIPOLEMOMENT)
CLS critical volume (VCRIT), dipole moment
Chung-Lee-Starling (DIPOLEMOMENT)
SuperTRAPP models critical volume (VCRIT), dipole moment
(DIPOLEMOMENT)
Macleod-Sugden (MCS parachor (PARACHOR)
and MCSA)
Costald saturated liquid density
Liquid viscosity mixing liquid viscosity
rule
Vapour viscosity mixing vapour viscosity
rule
Liquid thermal liquid thermal conductivity
conductivity mixing rule
Vapour thermal vapour thermal conductivity
conductivity mixing rule
Surface tension mixing surface tension
rule
Linear Gradient Theory Saturated liquid surface tension (STENSION)
Diffusivity – Fuller's chemical formula (FORMULA), UNIFAC
method subgroup structures (UNIFAC).
Diffusivity - Hayduk- critical molar volume (VCRIT), normal boiling
Minhas method point (TBOIL), parachor (PARACHOR) dipole
moment (DIPOLEMOMENT), saturated liquid
density, 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
It is possible to define a number of stream types in Multiflash. Each stream type
consists of a subset of all the defined components and may be associated with its
own set of models. The stream type concept is not particularly useful in the
Multiflash GUI. It is primarily intended to support process simulation
applications where different sets of components (with different models) may be
present in different unit operations or sections of a flowsheet.
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 the Multiflash GUI. However,
using the GUI, the composition of a sub-stream cannot be changed without
altering the composition of the overall stream and it is difficult to show a
realistic practical application in the GUI.
Initially we have defined an input stream containing 4 hydrocarbons, a petroleum
fraction, water and MEG 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.

We will first define a stream type called ‘Overall’ that contains all the
components. Enter the name, make sure the ‘All components’ option button is
selected and click Define Stream Type.
Click Close to return to the Select Models dialog.
A second stream can be defined the same way. This time we have selected the
NRTL VLE model. Click the ‘Selected components’ option button, select water
and MEG and enter the stream name ‘MEG’.
Click on Define Stream Type, then Close and Close again to return to the
Multiflash main window.
You can use the Tools/Show/Streamtypes menu item to display the list of
defined stream types.
show Sts;
NO. OF STREAM TYPES 2
1 OVERALL
2 MEG
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 Types/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 42. The most common are methanol, ethanol,
MEG, DEG, TEG and salts. Any of these can be included in the component list
and their composition defined as shown in “Specifying compositions” on page
137. Indeed this is the way you should specify isopropanol, propylene glycol and
glycerol. However, for methanol, ethanol, glycols and salt you can also use the
Inhibitor Calculator.
Inhibitor calculator: alcohols/glycols

The Inhibitor Calculator is included to simplify the addition of common
inhibitors. It is designed to calculate the amount of inhibitor or inhibitors to be
added to the amount of water present in the mixture in order to reach a user-
defined inhibitor concentration. This concentration may be specified in mass,
molar 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 amounts.
To calculate the amount of methanol, ethanol or glycols relative to the amount of
pure water present in the mixture:
From the Tools menu select Inhibitor Calculator and click on the
Alcohols/Glycols tab.

Select a databank for the pure component properties; INFODATA is the default.
If you have already defined the amount of water in the stream it will be shown in
the dialog box. Otherwise, you must first enter the amount of water to which the
inhibitor is to be added. The units for the amount of water are the currently
selected units for component amounts and may be changed by clicking on the
Units button.
You can specify the amount of inhibitors as a mass %, mole % or volume % (at 1
atm and 60ºF). The concentration specified is the concentration of each inhibitor
as a percentage of the total amount of water plus inhibitors. In the example
shown below the amount of methanol added will be 10% by mass of the total
amount of (water + methanol + MEG).
Click the Add button. The components will be added to the component list with
the amounts as specified. The total percentages of all inhibitors must sum to be
less than 100.
Click Close button to return to the main window.

The inhibitors are added in the selected input units for amounts even if the
concentration is specified in other units.
Note that specifying a given concentration of inhibitor (relative to water plus
inhibitors) does not mean that this will be the concentration in the aqueous phase
when the mixture is flashed. The inhibitor components and water will partition
between all phases present. For example, methanol will typically be present to a
significant extent in the oil and gas phases as well as in the aqueous phase.
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 Solid Freeze-out
model”“Pure solid phase” on page 49.
Salt calculator
The salt calculator provides a way of specifying the concentration of various
salts in water using commonly-reported laboratory measurements. You can
include the ions in your component list by selecting them from INFODATA.
However, an easier approach is to use the “Salts / Ions” tab in the Inhibitor
Calculator.
Electrolyte model
The electrolyte model is a detailed model of the ionic species in mixed
electrolyte solutions. It includes the following ions: Na+, K+, Ca++, Cl- and Br- .
The effect of other ions is obtained by determining an equivalent amount of
those listed. Alternatively, the RKSA-Infochem model can deal with ions by
defining an equivalent amount of salt pseudo-component.
The water content of your mixture can be defined from Select Components and
the Composition box, or entered on the Alcohols/Glycols tab as described above.
Click on the “Salt / Ions” tab. You can then define your salt from:

an Ion Analysis table
a Salt Analysis table

or the total amount of dissolved solids.
Clicking on the Add button initiates the calculation of the amounts of salt
pseudo-component or Na+, K+, Ca++, Cl- and Br- ions to be added to the
mixture in the input units set for amounts.
In the cases of an ion analysis or a salt analysis you can choose to express the
salt concentration in terms of equivalent amounts of salt pseudo-component,
Na+, K+, Ca++, Cl- and Br- ions, or just in terms of Na+ and Cl- ions by
clicking the corresponding option button.
Clicking on the Add button will display a table of the salts added, e.g.
The corresponding ions or the salt pseudo-component will be added to the list of
components in Multiflash and the amount of salt pseudo-component or of each
ion will be entered in the Composition drop-down table.
If you define only negative or positive ions in an Ion Analysis table an error
message will be displayed.

If you try to add more salt than is physically realistic the Salt Calculator does not
generate a warning but the amounts of the ions may be not realistic.
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 button.
In the case of adding ions explicitly (i.e., not salt pseudo-component), the
electrolyte model can only be selected as part of the hydrate model, i.e. in
conjunction with the CPA fluid phase model. The model selection is made using
the Hydrates tab in Select Model Set dialog.
If you have added ions to the mixture and then select a model that does not
include the electrolyte model a warning is displayed. For example
If you have selected a fluid phase model that does not include the electrolyte
model and then use the salt calculator to add ions a warning will be displayed.
If you wish to add both inhibitors such as methanol and salts you should enter
the required concentrations in the Alcohols/Glycols tab and then the salts in the
Electrolyte Model tab. Clicking on Add will then add the correct level of chosen
inhibitors and ions.
Troubleshooting - components
Databank not found

All licensed databanks will be placed 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 databank files: check for correct file
name and location.
The path used by Multiflash to find databank files is set in the Preferences
Window under Folders. Initially this will be the installation directory but you can
change the path if you have moved the databank to another location.
Databank not licensed

If you have not licensed DIPPR then warnings will appear.

If you have an earlier version of DIPPR and try to run Multiflash with the latest
version, then following error message will appear.
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 the selected databank. 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
If a component is not present in the INFODATA databank you should try the
DIPPR databank if you have a license. If you are planning a study and find that a
component is missing please check with Infochem. We may be able to locate the
required data.
TIP If the component you cannot find in 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 200. If you try to select more components 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 that have been analysed in great
detail.

Petroleum fluids
Introduction
Petroleum fluids are typically complex mixtures consisting of many thousands of
hydrocarbon components. It is not practical to identify all these components by
analytical methods. Even if it were possible to carry out an analysis it would not
be feasible to model the physical properties of the fluid by including all the
identified components.
The practical approach adopted in the oil and gas industry is to base the model of
a fluid on limited compositional analysis and other standard tests that are carried
out by commercial PVT laboratories. In this section we describe how to use the
information in a PVT laboratory report to construct a compositional fluid model
in Multiflash; this is what is meant by the term characterisation. Characterising
a petroleum fluid is an essential pre-requisite to studying the phase behaviour
and other properties of the fluid. Many applications are discussed in the Case
Studies that are included in this User Guide.
The objectives of the Multiflash characterisation procedure can be summarised
as:
 To make optimum use of measured data.
 Construct a compositional model that is not restricted to a
particular thermodynamic model.
 Ensure that phase behaviour calculations not sensitive to the
number of pseudocomponents.
 Achieve high fidelity based on compositional information.
 Allow model tuning to reproduce reliable experimental
measurements.
PVT Lab Analysis input

The primary information in a PVT lab report is a compositional analysis of the
fluid. This analysis is normally carried out by gas chromatography. The gas and
liquid from a separator test or bottom-hole sample are analysed separately and
the results are usually recombined to give a reservoir fluid composition. The
lighter hydrocarbons such as methane, ethane, propane etc. are individually
identified along with some inorganic compounds such as nitrogen, CO2 and
H2S. The analysis for hydrocarbons with more than 6 or 7 carbon atoms is
generally reported as single carbon number fractions (SCNs) which are actually
represent compounds in boiling point ranges. For example, a C9 SCN contains
all hydrocarbons that boil between the normal boiling point of n--octane + 0.5ºC
User Guide for Multiflash for Windows Petroleum fluids  89

and the normal boiling point of n-nonane + 0.5ºC. The analysis stops at a certain
C-number which is reported as a plus fraction. The plus fraction amount contains
all the material in the heavy end of the fluid and often represents a substantial
proportion of the fluid.
A typical example of a reservoir fluid analysis is shown below. It extends to
C36+
Component Flashed Liquid Flashed Gas Reservoir Fluid
Mole % Weight % Mole % Mole % Weight %
H2 Hydrogen 0.00 0.00 0.00 0.00 0.00
H 2S Hydrogen sulphide 0.00 0.00 0.00 0.00 0.00
CO2 Carbon dioxide 0.00 0.00 3.32 1.95 0.88
N2 Nitrogen 0.00 0.00 1.88 1.11 0.32
C1 Methane 0.00 0.00 35.52 20.86 3.45
C2 Ethane 0.08 0.01 12.11 7.14 2.21
C3 Propane 0.82 0.20 18.66 11.30 5.13
iC4 i-Butane 0.51 0.17 4.29 2.73 1.64
nC4 n-Butane 1.84 0.60 9.62 6.41 3.83
C5 neo-Pentane 0.00 0.00 0.03 0.02 0.01
iC5 i-Pentane 1.48 0.60 3.14 2.45 1.82
nC5 n-Pentane 2.36 0.95 3.67 3.13 2.33
C6 Hexanes 5.10 2.46 3.23 4.00 3.55
Me-Cyclo-pentane 1.60 0.75 0.60 1.01 0.88
Benzene 0.24 0.11 0.09 0.16 0.12
Cyclo-hexane 2.12 1.00 0.91 1.41 1.22
C7 Heptanes 6.27 3.51 1.13 3.25 3.35
Me-Cyclo-hexane 3.76 2.07 0.61 1.91 1.93
Toluene 1.54 0.79 0.22 0.76 0.72
C8 Octanes 7.57 4.85 0.54 3.44 4.05
Ethyl-benzene 0.59 0.35 0.03 0.26 0.29
Meta/Para-xylene 1.97 1.17 0.07 0.85 0.93
Ortho-xylene 0.72 0.43 0.02 0.31 0.34
C9 Nonanes 6.40 4.60 0.23 2.78 3.67
Tri-Me-benzene 0.72 0.48 0.00 0.30 0.37
C10 Decanes 6.99 5.57 0.07 2.93 4.29
C11 Undecanes 5.90 4.86 0.01 2.44 3.70
C12 Dodecanes 4.73 4.26 0.00 1.95 3.24
C13 Tridecanes 4.55 4.46 0.00 1.88 3.38
C14 Tetradecanes 3.71 3.95 0.00 1.53 3.00
C15 Pentadecanes 3.70 4.26 0.00 1.53 3.24
C16 Hexadecanes 2.79 3.46 0.00 1.15 2.63
C17 Heptadecanes 2.36 3.13 0.00 0.97 2.37
C18 Octadecanes 2.28 3.21 0.00 0.94 2.44
C19 Nonadecanes 1.97 2.89 0.00 0.81 2.20
C20 Eicosanes 1.56 2.41 0.00 0.65 1.83
C21 Heneicosanes 1.37 2.23 0.00 0.56 1.69
C22 Docosanes 1.21 2.06 0.00 0.50 1.57
C23 Tricosanes 1.07 1.91 0.00 0.44 1.45
C24 Tetracosanes 0.97 1.80 0.00 0.40 1.36
C25 Pentacosanes 0.87 1.69 0.00 0.36 1.28
C26 Hexacosanes 0.75 1.51 0.00 0.31 1.15
C27 Heptacosanes 0.69 1.45 0.00 0.29 1.10
C28 Octacosanes 0.63 1.36 0.00 0.26 1.04
C29 Nonacosanes 0.59 1.33 0.00 0.24 1.01
C30 Triacontanes 0.55 1.27 0.00 0.23 0.97
C31 Hentriacontanes 0.50 1.21 0.00 0.21 0.92
C32 Dotriacontanes 0.42 1.04 0.00 0.17 0.79
C33 Tritriacontanes 0.40 1.02 0.00 0.16 0.77
C34 Tetratriacontanes 0.35 0.93 0.00 0.15 0.71
C35 Pentatriacontanes 0.28 0.75 0.00 0.11 0.57
C36+ Hexatriacontanes plus 3.12 10.88 0.00 1.29 8.26
_____ _____ _____ _____ _____
Totals: 100.00 100.00 100.00 100.00 100.00
C36+
Molecular Weight (g mol-1) 625
Density at 60°F (g cm-3) 0.9925
90  Petroleum fluids User Guide for Multiflash for Windows

To enter the compositional data into Multiflash click on the button or the
Select/PVT Lab input menu item.
The following sections describe how to use this form.
Component list
A list of possible components is provided based on what is typically reported by
a PVT laboratory. The data for real components is taken from the databank
specified at the top of the form. From C9 onwards the list contains SCNs. The
real components in the list may be configured to your requirements.
If there are components included that do not appear in your analysis they may be
ignored or, if you prefer, they may be deleted by selecting them and clicking the
Component Delete button.
If you have additional components that you wish to add put the cursor in the
component cell above which you wish to add a new compound and click on
Component Insert button above the composition table. You will be able to
select from a list of valid components:

By default the “Databank Component” option is selected, but blank lines can be
inserted in order to add more petroleum fractions, for example, C120, if
necessary.
Only hydrocarbons can be added to the component list in the PVT Analysis. If
you try to characterise a fluid with a non-hydrocarbon component such as
acetone, the analysis will fail with 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 component 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 either a positive or zero amount then an error message will be generated
when you try to do the characterisation.
When carrying out characterisation of a mixture with a misspelled component

name or with the component which is not in the data source of your choice
another error message will be generated.

Only one data source 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 data source 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 location of the MFCONFIG.dat file is set under
Tools/Preferences/General, and will be the same path as for the Problem Files
(.mfl).
The mfconfig.dat file is an ASCII text file that needs to contain the following
type of instructions.
The file must start with the keywords “pvtanalysis info components” in that
order separated by blanks. Then the user types in the names of the components to
be displayed. Single carbon number cuts are specified by the letter “C” followed
by the carbon number. The ampersand is shorthand for creating a list of single
carbon number cuts, so in this example “C6 & C100” creates a list of all the cuts
from C6 to C100 inclusive. The ampersand can only be used once before the last
name in the list of components. The file must be terminated with two
semicolons.

Petroleum fluid composition
How you enter the petroleum fluid composition will depend on the information
supplied by the PVT Laboratory.
If you have a recombined reservoir fluid analysis (as shown above) you should
use the ‘Single Fluid’ input. If possible, enter the compositional data in mass
units rather than molar units. The reason for this is that the GC analysis measures
compositions by mass rather than by moles and it is best to use values that are as
close as possible to the actual measurements.
If you only have the separator gas and separator liquid analysis you should use
the Liquid+Gas tab on the form as shown below.
In this case it is necessary to enter the correct value of the recombination gas-oil
ratio (GOR) as reported by the laboratory. Often there are several GORs reported
that refer to different separators and it is essential to make sure that the
appropriate value is used. The gas composition may be entered in either molar or
mass units since all the gas phase components have a well-defined molecular
weight. The liquid phase composition should be entered in mass units if possible.
It is usually best to use the reservoir fluid composition provided by the
laboratory because this avoids the complication of recombining the gas and
liquid.
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 updated. 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 pseudo components 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 analysis is saved or

recalled, zero amounts will be allocated for SCNs where no composition was
provided.
You can paste fluid compositions into the PVT Analysis form. For example, if
you receive your report from the PVT laboratory as an Excel spreadsheet, then
provided your PVT Analysis component 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.
Molecular weight and specific gravity

It is usually helpful to provide additional information on the molecular weight
(MW) and specific gravity (SG) of the fluid. If you have entered a single fluid
composition the options are:
For the Liquid+Gas input the ‘Single fluid’ field is replaced by a ‘Total liquid’
field.
SG is the specific gravity relative to water at 60ºF and 1 atm. It is also possible
to specify the density in API degrees. You can convert from API gravity to SG
gravity using the following formula:
SG = 141.5/(API + 131.5)
The MW and SG of the Stock Tank Oil (STO) can be measured quite reliably
and are the best values to enter. The properties of the heaviest SCN (plus
fraction) are not normally measured and are obtained by calculation. The values
should not be used unless no other information is available. If none of these
values is supplied Multiflash will estimate the values based on the fluid
distribution you have supplied.
Our general advice is that if you have a lean gas or light condensate, i.e. where
the C6+ fraction is only a minor proportion of the total fluid, you should allow
the program to estimate the MW and SG. For heavier condensates with a detailed
analysis to C20 or above it is also probably better not to specify a MW. For oils
you should, preferably, enter the MW and SG of the STO as these are usually
measured values.
In order to provide some guidance when running Multiflash we have supplied
some warning messages. If the molar fraction of C6+ is <0.5 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 > 0.5 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 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 still 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.
Total amount of fluid

If you wish to specify the total amount of fluid that will be generated you can do
this by entering a value in the ‘Total amount of fluid’ box. You can choose the
units from the drop-down list. The value does not affect the composition; it is
simply used to scale the amounts.
If the amount is left blank the amount generated depends on the way the
composition is entered. For example, if the composition is entered in mass units
and the sum is 100 then 100 g of fluid will be generated.
If a water cut is specified (see below) the total fluid amount will include the
water.

Water cut
The Water Cut box allows you to add water to the fluid. The amount can be
specified as a volume percent of the hydrocarbon liquid phase at standard
conditions (60 ºF, 1 atm).
You should note the following points
 The procedure used is approximate but does allow for loss of water
to the vapour phase.
 If you have already defined an aqueous phase by using the inhibitor
calculator (or otherwise), entering a water cut value will alter the
amount of water in the mixture but leave the composition of
inhibitors unchanged, effectively altering the inhibitor
concentration.
 Entering 0% for the Water cut will leave water in the component
list but overwrite any existing water amount by zero concentration.
 Leaving water cut blank will leave any aqueous phase already
defined unaffected.
Adding water will not affect the hydrocarbon fluid characterisation although it
may affect the subsequent phase equilibria calculations.
As an alternative you can specify the water cut as part of the petroleum fluid
property matching: see “Matching dew and bubble points” on page 116.
Total Wax Content

The Total Wax Content box provides the simplest means to enter information
which can be used to model waxing behaviour. Modelling fluids including wax
is discussed in the section “Case studies – Wax precipitation” on page 260.
The Total Wax Content is the total amount (in mass) of C20+ n-paraffins (
relative to Stock Tank Oil) that is determined using the industrial standard UOP
Method 46, where the wax is precipitated by addition of a polar solvent such as
acetone.
In Multiflash, the Total Wax Content is used to estimate the n-paraffin
distribution in crude oils, that is required by the Coutinho wax model for
modelling wax phase behaviour. If neither n-paraffin distribution nor the wax
content is measured, an empirical correlation can be used to estimate the total
wax content by ticking the Estimate Wax Content box, from which a n-paraffin
distribution can be established. However this estimation method should only be
valid for oils and only be used if no other information is available.
If either measured wax data or the estimation method is specified, the
characterisation procedure will generate both n-paraffin components and non-n-
paraffin pseudocomponents. However, to model the solid wax formation, the
wax model must be selected from the Select Model Set dialog.
The recommended analytical information for modelling wax is a measured n-
paraffin distribution and this input is described in the section “PVT Lab Analysis
input with n-paraffin analysis” on page 105.
SARA Analysis
A SARA(Saturates, Aromatics, Resins and Asphaltenes) analysis is the industry
standard fractionation method for dividing crude oils into four components
according to their polarizability and polarity. The analysis is usually expressed in
mass % relative to the stabilised oil.

The SARA analysis is used to characterise resin and asphaltene components that
are used by the asphaltene model. The asphaltene modelling procedure is
discussed in the section “Case studies – Asphaltene flocculation” on page 267.
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 box.
However, we recommend that you should use the measured values if at all
possible.
The SARA analysis values should only be entered if you intend to use the
Multiflash asphaltene model. Other models may produce results with the
asphaltene and resin components but will not give the correct phase behaviour.
Pseudocomponents
The Pseudocomponents section of the form provides control on how the
petroleum fraction pseudocomponents are generated.
The ‘Start pseudocomponents at’ box sets the lowest SCN at which to generate
lumped pseudocomponents, i.e. pseudocomponents that represent a group of
SCNs. The default setting is C6 but it may be changed using the scroll buttons.
For example, if set to C10 this means that C6, C7, C8 and C9 will be represented
by individual pseudocomponents and lumped pseudocomponents will start at
C10.
The smallest SCN from which you can start the pseudo component split is C6.
The largest number depends on the carbon number distribution and on the SCN
components defined in the component list. If you try to start from a larger SCN
than the heaviest SCN in the component list you will get a warning:
If you wish to start the pseudocomponent split at a larger SCN than the heaviest
SCN you will need to add additional SCN components to the component list.
The ‘Number of pseudocomponents required’ box sets the number of lumped
pseudocomponents that will be generated. The default value is 15 but in many
cases a smaller number of lumped pseudocomponents will be quite adequate.
The maximum number of components in Multiflash is 200. If you input a larger
number of pseudo components than that Multiflash will change it to 200.
If a wax content has been specified the corresponding boxes for n-paraffin
pseudocomponents will be active. The default setting and recommended value
for the n-paraffin pseudo-components is 15.

Characterisation
The characterisation procedure is started by clicking on the ‘Do
Characterisation’ button. If the inputs provided are consistent with the
requirement of the fluid characterisation in Multiflash, you will see a message to
indicate that the characterisation has been successfully completed
The carbon number distribution entered and the function used to extrapolate the
heavy end will be displayed.
The values can be exported to Excel by Clicking the “Write To Excel” button on
the plot form.
If you do not wish to see this plot then it can be disabled by unchecking the
“Display SCN distribution” check box in the bottom left-hand corner of the PVT
Lab Analysis form.
Close the Carbon Number Distribution plot and the PVT Lab Analysis form. The
components and amounts generated will be displayed in the main window. For
example

The numbers in the first column are simply sequence numbers for the
components. Pseudocomponents have a P appended to the number. The second
column contains the component name. Lumped pseudocomponents are allocated
names that correspond to the carbon number range, eg. C6-19. The third column
gives the amount of each component in the selected input units. The final column
shows the lower- boundary for the SCNs included in each lumped
pseudocomponent.
User Defined Cuts

Multiflash will automatically adjust the boundaries between the lumped
pseudocomponents to give the optimal approximation to the full SCN
distribution for the number of pseudocomponents specified. However, you can
also control the boundaries between the pseudocomponents by ticking ‘User
Defined Cuts’ and pressing the ‘Define Cuts’ button. A drop-down box allows
the user to define the required boundaries as carbon numbers. These carbon
numbers represent the point in the distribution where one pseudo component
finishes and the next one starts; they are the lower boundaries of each pseudo
component, not the average carbon number of the pseudo component.
The following example, showing part of the ‘PVT Analysis’ form, illustrates a
case where the user wishes the distribution to split above C10. The boundaries
are set at 10, 15, 20, 30 and 40 allow the user to create the following pseudo
components: C10-15, C15-20, C20-30, C30-40 and C40+. Note that when you
specify the carbon number boundaries, the first boundary determines where the
pseudo components must begin, and it overrides the entry in the box ‘Start
pseudocomponents at’

If you leave all the entries blank in the carbon numbers drop-down box,
Multiflash estimates the pseudo component boundaries automatically, just as if
you had not specified user-defined cuts. If you only partially fill the carbon
numbers box, generation of pseudo components stops when a blank entry is
encountered.
Multiflash also expects that the carbon numbers will be entered in a sequence of
increasing values. If this is not done, some entries will be skipped, and a reduced
number of pseudo components will be produced.
The carbon numbers must all be greater than 5.5. Attempt to input a smaller the
following warning will be triggered.
The facility allows you to define compatible pseudo components for several
fluids with the same carbon number ranges.
Saving a PVT Analysis

Before you can save your PVT 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.
Black Oil Analysis

In some circumstances a user may have very limited compositional data for a
fluid. A compositional analysis may not have been measured or the data may
have been generated from another application.
The Black Oil analysis provides a way of constructing a compositional fluid
model from limited data.
The Black oil input is the third tab in the PVT Lab Fluid Analysis form.

Input data
The minimum data required are:
 Gas gravity. This is the MW of the gas divided by the MW of air
(28.964).
 Stock Tank Oil specific gravity SG (relative to water at 60ºF).
 Solution GOR: the amount of gas relative to oil at standard
conditions.
Additional data that may be entered if available but is optional:
 Watson K-factor for the oil.
Kw = (Tb)1/3 / SG, where Tb is the boiling point in ºR
 Gas Analysis. The gas analysis need not be complete; only the
mole percentages of the components named on the form can to be
entered, and they need not sum to 100%.
Other inputs are as for the compositional PVT Analysis.
Distillation curves
Distillation curves are generated by standard experiments that report the amount
of an oil that is distilled as a function of temperature. They are more common for
refinery applications than in the upstream oil industry. The fourth tab on the
PVTLab Fluid Analysis form may be used to enter either TBP data or D86 data.
TBP distillation
True boiling point (TBP) distillation is the default distillation type on the
‘Distillation Curves’ tab.

The TBP values are entered against the cumulative amount distilled as a volume
percent. The temperature units can be selected using the drop-down list on the
form. The molecular weights and specific gravities are optional and need only be
entered if they have actually been measured. Note that they describe a TBP cut;
for example the cut from 0% to 10% by volume has a molecular weight of 136
and a specific gravity of 0.782. However, the TBP of 165.6 °C corresponds to
0% distilled off and 176.7 °C corresponds to 10% distilled off, so the first cut is
that which distils between 165.6 and 176.7 °C.
By clicking the ‘Do Characterisation’ button, the characterisation proceeds in the
same way as for a standard compositional analysis except that the result of the
regression is conventionally expressed in terms of cumulative amounts as shown
below for the same example.

If the software cannot represent the data then a warning message will be shown
to indicate that the characterisation procedure has failed. It may be that the data
has been entered incorrectly or is inconsistent.
ASTM D86 distillation

D86 is a standard analytical procedure that resembles TBP distillation but is
simpler. The oil sample is placed in a single vessel and progressively heated to
drive off gas. To enter a D86 analysis, the ‘Distillation Curves’ tab is used as
above, but the D86 radio button is selected. The cumulative volume distilled is
entered in the table together with the temperatures, but unlike TBP curves, there
is no option for entering molecular weights or specific gravities as these cannot
be measured by the D86 procedure. The example below illustrates a D86
analysis.
Multiflash converts D86 curves into an equivalent TBP curve using the method
of Riazi and Daubert which is described in Analytical Correlations Interconvert
Distillation Curve Types from Oil & Gas Journal, 84, 50, 25 August 1986. The
resulting TBP curve is then characterised on pressing the ‘Do Characterisation’
button. The regression for this case is shown in the following plot.

PVT Lab Analysis input with n-paraffin analysis
For modelling phase behaviour including waxes the input information should
ideally include a compositional analysis of the fluid plus an analysis of the n-
paraffin content. There is a separate PVTLab Fluid Analysis input form to
handle this sort of data. In order to have a reliable and realistic description and,
therefore, better performance of the characterisation procedure, the distribution
of heavy paraffinic components well beyond nC20 would be desirable to give a
realistic prediction by the characterisation procedure.
To characterise a waxy crude with n-paraffin distribution, click on the

toolbar button or use the Select/PVT Input for n-paraffins menu item. The form
has four tabs which allow for different types of fluid and n-paraffin analysis.
n-Paraffin distribution
In the first tab the total fluid composition is entered as for the standard PVT
analysis in mole or mass percent, which would be expected to add to 100%. If it
does not a warning message provides the opportunity to normalise it. The n-
paraffin distribution is that measured for the STO, again in mass or mole%.
These units can be set independently of those used for the total fluid. The n-
paraffin distribution in the stock tank oil would normally be expected to sum to
substantially less than 100%. We check that the total for the n-paraffins is less
than 100%.

The second tab allows for n-paraffin data which have been measured differently.
In this case the total fluid composition is entered in the normal manner as mole
or mass percent. However, the n-paraffin distribution is described as the fraction
of each individual SCN (single carbon number cut) above C6 which is n-
paraffin. In this case the unit, mass or mole, for the n-paraffin distribution must
match that of the Total fluid composition – and the unit heading will reflect this.

The remaining two tabs operate the same way but allow for the overall fluid to
be described in terms of gas plus liquid with a recombination GOR. In this case
the fraction of n-paraffin will be that proportion of the liquid phase rather than
the overall fluid.
In any case if you try to enter an n-paraffin fraction or percentage for cuts below
C6 a warning message will be issued.
Characterisation
You can control the starting point for n-paraffin lumped pseudocomponents and
the number of lumped n-paraffin pseudocomponents in a similar way to the
procedure described on page 98.
The default starting point for n-paraffin pseudocomponents is N6 (n-paraffin
with 6 carbon atoms) and the default number of lumped n-paraffin
pseudocomponents is 15. It may be possible to use fewer pseudocomponents but
if the number is too small the wax phase will not be well-described and
Clicking on the Do Characterisation button will analyse the data and start the
characterisation procedure. The measured and fitted distributions are displayed
for n-paraffins and non-n-paraffins if the compositions are given in a same unit.
An example is shown below.
After closing this form and the PVTLab Fluid Analysis form the list of n-
paraffin and non-n-paraffin pseudocomponents is displayed in the main window.

The n-paraffin pseudocomponents are denoted by an N prefix, eg. N6-8. The
non-n-paraffin pseudocomponents are denoted by an I prefix, eg. I6-22. The
number after the prefix indicates the carbon number range that the pseudo-
component is based on.
Estimated n-paraffin distribution

If you do not a have measured n-paraffin distribution Multiflash can estimate the
distribution and generate n-paraffin pseudocomponents. On the standard
PVTLab Fluid Analysis form you can specify the wax content, or get Multiflash
to estimate the wax content; see “Total Wax Content” on page 97.
The starting point and number of n-paraffin pseudocomponents should be

specified as described above.
Clicking on the Do Characterisation button displays a warning that the n-paraffin
distribution will be estimated

Troubleshooting – PVT Analysis
This section describes some common problems that may be encountered.
Sensitivity to characterisation
Not all the PVT analyses we have tested are well reproduced by the PVT
characterisation fitting method. If this happens, it may be due to the
inconsistency between the SCN distribution and the information for the
molecular weight and/or specific gravity for the plus fraction or STO or total
fluid. If you do see a warning related to the inconsistency, use the phase
envelope tracer to see how the phase envelope is affected by characterising the
fluid with and without the information for the molecular weight and/or specific
gravity.
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.
Defining petroleum fractions

If the petroleum fractions in your mixture have been pre-assigned, their
properties and amounts can be entered directly using the "Add/Remove
Petroleum fractions" input form from the Select Components form. The most
common reason for doing this is to re-use a characterisation from another
application such as a process simulation package.
Basic characterisation properties

The list of properties that may be used to support characterisation of petroleum
fractions is:
Component name
Carbon number
Molecular weight (g/mol)
Specific gravity at 60ºF relative to water at 60ºF
Normal boiling point
Critical temperature
Critical pressure
Pitzer’s acentric factor
However, not all of these are necessary. The minimum input sets are the
component name together with the carbon number or molecular weight or
specific gravity or boiling point or the information of critical temperature,
critical pressure and acentric factor. Other properties that are not specified will
be calculated by Multiflash.

Other properties
The properties that are estimated, if they have not been provided, are:
Carbon number
Molecular weight
Normal boiling point
Critical temperature
Critical pressure
Critical volume
Acentric factor
Parachor
Dipole moment
Enthalpy of formation
Standard entropy
Melting point
Enthalpy change on melting
Entropy change on melting
Heat capacity change on melting
Perfect gas Cp
Saturated liquid density
Saturated vapour pressure
Enthalpy of evaporation
Liquid Cp
Liquid viscosity
Liquid thermal conductivity
Vapour viscosity
Vapour thermal conductivity
Surface tension
Entering petroleum fractions

Click on the Select Components toolbar button or choose the Select/Components
menu option.
You will probably wish to define a number of pure components as already
described in the section “Defining a mixture” on page 65.
To define a petroleum fraction click the “Add/Remove Petroleum fractions”

button to launch the Petroleum Input form.

If you have a pseudo component reported to be, say, C7 but have no physical
properties for this cut you can simply type in the component name, e.g. C7, and
the carbon number, in this case 7 then click on “Calculate” button. The
remaining physical properties required to characterise the fraction will be
calculated by Multiflash using the industry standard correlations of petroleum
fraction recommended by Riazi and Al-Sahhaf.
On the form, the user-entered values are displayed in red and the values
calculated by Multiflash are in black. By default the type of petroleum fraction,
that is given in the form under the Extended properties Tab, is set to Normal.
Click the OK button to close the form.
If not all the properties are known, the rest of the physical properties for the
petroleum fractions will be estimated by Multiflash and displayed in black as
shown below.

The default display for the number of petroleum fractions on the form is set to 25
but the maximum number of petroleum fractions can be entered in this form is
100. After defining the petroleum fractions, click OK button or click the
Calculate button to define the fractions in Multiflash before closing the form.
If a set of characterised petroleum fractions are needed to be defined, this new
Petroleum Input form allows you to import the physical properties by copying
and pasteing from Excel spreadsheets. To do this, right-click the mouse to select
the options to do the Copy and Paste on the form.
Note that there is a Units button available in the Petroleum Input form. Check
the units before entering data to define the fractions.
The reference for the physical property correlations: Riazi, M.R. and Al-Sahhaf,
T.A., Fluid Phase Equilibria 117 217 1996.
Editing petroleum fraction data

Having defined your petroleum fractions 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 by going to the Petroleum Fraction Input form.
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
On the Select Components form, click the “Add/Remove Petroleum fractions”
button to open the Petroleum Fraction Input form. On the form all the necessary
physical properties of the defined petroleum fraction will be displayed. 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 Calculate button or OK button to update the physical properties of the
fractions in Multiflash so that the new or modified 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. This should be
done using the Tools/Pure Component Data option and changing the stored
property value. If you change the molecular weight of a petroleum fraction this
way then the critical properties of the fraction will not be re-calculated.
Deleting petroleum fractions

To delete one or group of petroleum fractions, highlight the row or rows on the
Petroleum Fraction Input form and then right-click the mouse to select the Delete
Selected Rows option.
To confirm the deleting click the Yes button on the following message dialog.

Then click the calculate button to update the component properties or OK button
to close the form. Please note that clicking Cancel button to close the form will
not load the change onto Multiflash and the petroleum fractions will not be fully
updated.
Problems defining a petroleum fraction

The properties you enter to characterise a petroleum fraction on the Petroleum
Fraction Input form will be checked when you click on the Calculate/OK button
on the form. If they are physically unrealistic or cannot be processed by the
petroleum fraction suite of correlations you will be warned and the warning or
error message may be given in a message dialog box or displayed on the main
window of Multiflash, and the fraction will not be accepted by Multiflash.
The obvious problems will be entering a negative number for a quantity which
must be positive, e.g. molecular weight, specific gravity, critical temperature and
pressure or acentric factor. The warning message will pop-up after the Calculate
or OK button is clicked.
The detailed message will be displayed on the main window.
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
170.
Delumping tool
The PVT Analysis tool in Multiflash is used to characterise a fluid based on an
existing analysis carried out in the PVT lab. As mentioned in the previous
chapter, the objective of the characterization procedure is to produce a mixture
of components that more closely describes the analysed fluid.
The produced components can be lumped into pseudocomponents in order to get
a simpler mixture while preserving the main characteristics of the fluid such as
bubble points.

If the fluid is characterized in Multiflash all the PVT analysis inputs are stored so
it is easy to re-characterized the fluid with different setting as necessary. For
example it may be needed to reduce or increase the number of pseudo
components or add other inputs such as the molecular weight of the fluid.
For any fluids characterized by a different software package, it is now possible to
re-characterize the fluids using the Delump Tool in Multiflash.
How to use the delumping utility

The delumping tool can be used with any previously characterized fluid. It can
also handle fluids where asphaltenes and waxes are present. In the case with
waxes the n-paraffin components will also be delumped.
To launch the Delump tool click the Delump button: . The following
window will appear if there is a current defined fluid.
The Current Fluid table (1) displays the components and amounts of the current
fluid. After delumping it will display the components and amounts of the
delumped fluid.
The Delumping status (2) shows the current status of the delumping tool. In this
case it shows that the current fluid is not delumped.
The Fluid summary (3) lists the number of components of each type:
 Real components: methane, ethane, etc
 Petroleum fractions: standard petroleum fractions, C6, C7, C7+, etc
 Normal paraffin fractions: fractions n-paraffin components, N6, N7,
N7+, etc
 Iso-paraffin: petroleum fractions that are not part of the n-paraffin
distribution, example I6, I7, etc

 Resin fractions: petroleum fractions constituted by resins, example R6,
R7, etc
 Asphaltene: the amount of the asphaltene component in the current
units.
The fluid is ready to be delumped. Click the “Delump” button. The resulting
fluid is displayed in the Current Fluid table.
NOTE: Any Matched information such as bubble points, dew points, density
will be discarded when the fluid is delumped.
The number of components of each type has increased and new options are now
available for the delumped fluid.
Clicking the “Revert” button puts the fluid in its original lumped state.
It is now possible to export the delumped fluid to the PVT Lab Fluid Analysis
tool by clicking the “Open PVT tool” button. It will open the standard PVT lab
Fluid analysis tool if no n-paraffins are present and the PVT lab Fluid analysis
with n-paraffin distribution tool otherwise.
If the fluid has no n-paraffin analysis, one can be added by ticking the “Add
n-Paraffin analysis” on the Delump Fluid form.
By ticking this option the “PVT lab Fluid analysis with n-paraffin distribution”
tool will open instead of the standard one.
After the PVT tool is opened the user has the option to change the number of
pseudo-components, add molecular weight, specific gravity, SARA analysis and
water cut if necessary and to re-characterise the fluid.

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 properties of the petroleum fractions to modify a
property of the overall mixture. Typical mixture properties that can be adjusted
by altering fraction properties are the dew and bubble points, the viscosity, the
volume/density and, when the model is available, the wax appearance
temperature. The asphaltene precipitation point is matched by adjusting the
model parameters rather than the properties of any fractions and will be
discussed in the relevant section.
Matching of dew and bubble points, bubble point/GOR/Water cut or
density/volume is only available with variants of RKS, PR or CPA model
options, although the flexibility and method of fitting will vary.
Matching dew and bubble points

Petroleum fraction can be re-defined by adjusting their properties to reproduce
known experimental data, e.g. the dew point or bubble point of a mixture.
The reflected changes of the properties of a petroleum fraction to re-produce the
dew or bubble point experimental data depend on the equation of state models
used when matching. If the RKSA, PRA, PR78A, or CPA models are used, the
vapour pressures of each of the pseudo components are modified. The
modifications are defined by two Mathias Copeman parameters. The keywords
saved to the .mfl file are model-dependent. For example the keywords
MCRKSA1 and MCRKS2 are for RKSA model, MCPRA1 and MCPRA2 for
PRA model. If other equation of state models are used (such as the standard
RKS) the acentric factor of the pseudo components are adjusted to match the
dew point or bubble point experimental data.
Matching is carried out using the Tools/Matching menu option. The matching
function works with any number of fractions.
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 fixed phase
fraction flash, see “Fixed phase fraction flashes” on page 144.
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 vapour pressure of the
fractions will be adjusted until the calculated and experimental values match.
A plot will show a comparison of the matched data to the experimental data -
and the unmatched calculations.

The two adjusted Mathias Copeman parameters 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 462.8 401.6 303.5 229.6;;;
PETROLEUM FRACTIONS PHYSICAL PROPERTIES:
TC/K PC/bar MC1 MC2
11P 515.614 31.2927 1.0045936 -0.12532595
12P 545.103 31.0298 1.0698024 -0.18301678
13P 570.756 29.346 1.142895 -0.23326444
14P 597.629 27.167 1.2325474 -0.28864297
15P 666.44 21.7559 1.5491369 -0.46237886
16P 734.346 17.2713 1.8226226 -0.62069818
17P 734.346 17.2713 1.8226226 -0.62069818
18P 734.346 17.2713 1.8226226 -0.62069818
19P 749.95 16.2654 1.9057277 -0.66510979
EXPERIMENTAL AND CALCULATED VALUES: DEWPOINT
T(exp)/K P(exp)/bar P(calc)/bar
305.35 462.8 450.52454
340.95 401.6 413.32432
398.55 303.5 319.64004
442.55 229.6 207.69892
where C17+ is the 19th component. The adjusted Mathias Copeman parameters
MCRKS1 and MCRKS2 for the RKSA model will be reflected in the pure
component record.

The new fraction properties can be saved using File/Save Problem Setup. The
second Mathias Copeman Parameter MCRKS2 values may not be displayed if
they do not result in a better fit to the dew point line or there is only one
dewpoint specified in the matching form.
Since Multiflash version 3.9 the matching facility for bubble points has been
expanded to include GOR, liquid density and optionally the water phase fraction
(Water cut). This is accessed through the Tools/Matching/Bubble Point/GOR
option.
If only bubble point data are available then these are entered using the bubble
point data table. If no bubble point data is available at all, it is still possible to
match GOR. To fit the GOR you must enter the conditions at which the supplied
GOR were measured and the GOR itself. The units may either be standard cubic
feet per barrel of liquid at the T,P specified or the equivalent in standard m3/m3.
The liquid density is optional but, if provided, must be at the same T,P
conditions as the GOR. The experimental value for water phase fraction has to
be expressed as volume percentage of the total liquid phase obtained at the
separator condition: hydrocarbon and water. A choice of units is provided for
liquid density including specific gravity in relation to water. The GOR and liquid
density units in the bubble point matching form are not affected if the Units
option is changed. The T,P units may be changed but in GOR conditions and
bubble point units must be the same. The plot will show the phase envelope
before and after matching with the information specified in the Match Bubble
Point / GOR Data form.
For the case with water cut specified in the matching, the phase envelopes for
both the unmatched and matched case are the fluid without presence of water.

The output in the results window will show the adjusted property values for each
of the properties matched, and the comparative values to experimental data. For
the bubble point matching the Mathias Copeman parameters are changed as
described for the dew point matching. For fitting to liquid density the Peneloux
shift parameters are altered as described below for density/volume matching.
The GOR and the water phase fraction are matched by changing the fluid
composition: change non-aqueous components to match GOR and change water
amount to match water cut. The output shows the original and adjusted
composition for each fluid component and the ratio of the two. The initial
amount of water will always be set to zero, even if it is not zero before using the
matching facility.

Although some warning messages are triggered, e.g. entering a GOR but without
T,P conditions, it is not possible to trap inconsistencies in the entered data. The
best way of spotting major inconsistencies is the comparison of the matched and
unmatched phase envelopes. If, for instance, the GOR is entered in the wrong
units then there may be a good match for bubble point, density and GOR but the
phase envelope change is significantly different and merits closer inspection of
the experimental data.
The ratio of adjusted composition to original data may also indicate possible
inconsistencies.
Similarly any GOR entered as part of the PVT Analysis and used to calculate the
recombined fluid composition is ignored for the purposes of Bubble point/GOR
matching and is not checked for consistency. Any amount of water added during
PVT characterization, where a water cut was asked, will also be discarded.

Major differences in the phase envelopes may indicate that it is worth checking
and eliminating inconsistencies.
Matching Density/Volume
The procedure for matching density/volume is similar to matching dew and
bubble points. The matching is flexible and, as with the viscosity, the phase to be
matched can be specified.
In this case the amended property values are the coefficients for the Peneloux
volume shift parameter.
match table volume OVERALL temperatures 381.15 381.15 381.15
381.15 350 350 350 350;pressures 360 350 340 330 100 80 60
40;Volume kg/m3 202.375 268.229 253.93 249.228 93 73 55 35;;;
PETROLEUM FRACTIONS PHYSICAL PROPERTIES: PENELOUX VOLUME
SHIFTS/(m3/mol)
CONST. TERM TEMP. DEP. TERM
10P 0.00171839 -4.31382E-6
11P 0.00198798 -5.00294E-6
12P 0.00222093 -5.58758E-6
13P 0.00241593 -6.07539E-6

14P 0.00261675 -6.57719E-6
15P 0.00283127 -7.11674E-6
16P 0.00309332 -7.77269E-6
17P 0.00328365 -8.24893E-6
18P 0.00353665 -8.88117E-6
19P 0.00387479 -9.72486E-6
20P 0.0042509 -1.06627E-5
21P 0.0047303 -1.18573E-5
22P 0.00514017 -1.28798E-5
23P 0.00526666 -1.31955E-5
24P 0.00557851 -1.39722E-5
EXPERIMENTAL AND CALCULATED VALUES: VOLUME

T(exp)/K P(exp)/bar Vol(exp)/kg/m3 Vol(cal)/kg/m3
381.15 360. 262.375 263.20947
381.15 350. 258.229 258.47254
381.15 340. 253.93 253.59631
381.15 330. 249.228 248.57439
350. 100. 93. 94.583391
350. 80. 73. 73.892152
350. 60. 55. 53.908961
350. 40. 35. 34.831117
Matching wax data/WAT

The method used for matching the wax precipitation curve or 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 Wax
Phase to activate the Wax data dialog box.
The table can be used to match WAT or the amount of wax precipitated for a
given pressure as the temperature falls. In the case of WAT you may wish to
give the amount of wax as zero mass(or mole)%, in which case it does not matter
of you specify the wax as a function of the oil plus wax phase or total fluid.
However, it may be more realistic to give a positive amount of wax that reflects
the nature of the measurement technique used. We recommend 0.045mass% for
CPM or 0.3mass% for DSC.
Once you have entered the data , click on the Match button and the melting
temperature and the enthalpy of melting of petroleum fractions will be adjusted
to match the information provided. The adjusted melting temperature or
enthalpies will be displayed in the main window.

After matching a plot will be generated but the type of plot depends on the data
entered on the form. If it is a set of wax precipitation data at a given pressure or
temperature, wax precipitation curves as a function of temperature/pressure are
plotted.
If the data are for a fixed wax phase fraction, the wax phase boundary line at the
fixed phase fraction is plotted.

The new fraction properties can be saved using File/Save Problem Setup for
future use. With the Coutinho wax model the adjustment is made only to the n-
paraffin pseudo-components as it is these which form the wax phase.
Matching liquid viscosity

This facility allows you to match a known total hydrocarbon liquid viscosity or
the stock tank oil viscosity. From the Tools/Matching menu select Viscosity.
Make sure LIQUID1 or LIQUID2 is selected from the list of possible phases and
enter the temperature and pressure conditions as well as the liquid viscosity data
to be matched. The matching procedure works by altering the reference viscosity
of the petroleum fractions and these will be reported in the main window,
together with a comparison of the experimental and fitted values of viscosity.
For example

Prior to this a comparison plot will be generated for 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
appears physically realistic. No warning will be issued if liquid viscosities
increase with increasing temperature.
Matching vapour viscosity

The same procedure given above can be applied to matching the viscosity of
vapour phase. There is only one vapour phase, GAS in this case. With a defined
viscosity model for both GAS and LIQUID, only one set of viscosity data of
either liquid or gas phase can be matched at a time for a typical fluid.

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.
Significant differences in the matched and unmatched phase envelopes when
matching multiple properties, such as bubble point, GOR and density, may
indicate inconsistent experimental data but this may not generate a warning
message.
Petroleum Fluid Blending

The blending option allows mixing, or blending, of already characterised
petroleum fluids to provide a new fluid characterisation, for example when two
pipes intersect.
The blending facility allows up to four separate fluids, each of which must be
defined in a problem file (.mfl) or be the current fluid in use in Multiflash , to be
blended together in relative amounts specified by the user to produce a new fluid
described by its own set of pseudo-components. The properties and relative
amounts of the blend’s pseudo-components are automatically calculated by the
Multiflash blending procedure.
To display the blending form, click on the button or the Tools/Blend Fluids
input menu item.

Blending method
The blending method first picks out the discrete components such as methane,
ethane, carbon dioxide, etc. from each fluid and adds them together in the correct
proportions. The method then picks out the dominant pseudo-components from
the mixture. It adds all the non-dominant pseudo-components to the most
physically similar dominant pseudo-components and averages the physical
properties of the resulting blended pseudo-components. The dominant pseudo-
components are those with the highest concentrations in the mixture for each
range of molecular weight and also those that occupy the extreme positions of
the molecular weight distribution. The method has the following advantages:
It is automatic and requires no user intervention.
It works for any type of fluid that can be represented in Multiflash and saved in
problem files, although it does work best if the fluids and the pseudo-component
distributions are similar.
The properties of the blend change smoothly with changing blend ratios. The
properties of the unblended fluids also change smoothly as small amounts of
other fluids are added, i.e. the method shows correct limiting behaviour.
The method of averaging the properties of the blended pseudo-components is
exactly the same as that used in the PVT analysis procedure to create the pseudo-
components used to represent the properties of the original petroleum fluids.
The method also handles waxy and asphaltenic crudes thereby predicting the
likely wax or asphaltene formation from the fluid blend.
For any volume blending, it is recommended that the fluid model is defined in
the original MFL files so that the density can be calculated at the standard or the
given condition if the density is not specified. Without knowing the density, the
volume blending will fail.
Fluid file name

The user can specify up to three different problem files describing different
fluids that are to be blended. In addition, the fluid that is currently loaded in
Multiflash can also be one of the fluids to be blended. The file names can be
directly entered in the text boxes, or alternatively the user can click on Browse to
search for each file in turn.

Fluid amounts
The relative amounts can be entered for each fluid in a variety of volume, mass
and molar units which can be selected from the drop-down list. If an amount is
left blank or set to zero, none of that fluid is added to the blend. So, if the fluid
currently loaded in Multiflash is not required in the blend, its amount is omitted
or set to zero.
If a volume unit is selected, the program needs to calculate the density of the
fluid as part of the blending procedure. The program uses the information
provided in the window ‘User Specified Conditions for volume blending’ to find
the fluid density. By default the ‘standard condition’ is ticked, in which case the
program uses the model defined for that fluid to calculate its density at standard
conditions (1 atm and 60degF). If no model is defined for that fluid, Wilson
correlation is used to estimate the K values and then the fluid is flashed at the
standard condition to find the fluid density.
If ‘standard condition’ is not ticked, the user has two other options. If the density
is entered, its value is used directly to calculate the blend ratio. Alternatively, if
the density is not specified but the temperature and pressure are, the program
uses the model for that fluid to calculate its density at the specified temperature
and pressure.
Note that the table for ‘User Specified Conditions for volume blending’ can only
be filled in if volume units are selected for the fluids.
Model definition
One of the fluids can be selected as providing the model definition for the fluid
blend. The models and phases defined for the blended fluid are then the same as
for the selected fluid. Likewise the information stored for all the associated
utilities such as matching, PVT analysis, the inhibitor and salinity calculator, etc.
will be taken from the same selected fluid. Alternatively, no fluid need be
selected in which case the definition of blended fluid will include only the
components and their properties with no associated model definitions or utility
information.
If the blended fluids are asphaltenic, the parameters of the asphaltene models for
each of the constituent fluids will be averaged to give a prediction of possible
asphaltene precipitation in the blend. However, to obtain this prediction the user
must select a model definition for one fluid as, if no models are selected, the
asphaltene model parameters will be lost.
Blending procedure
The blending procedure is initiated by clicking OK. If there is a fluid currently
defined in Multiflash, a warning will appear as follows:
On clicking Yes, the previous fluid definition is lost, and the blend becomes the
currently defined fluid. If No is clicked, nothing happens giving the user the
option to save the current fluid description, for example, before proceeding.
In the example below, 5 kg of fluid described in file PetFluid.mfl is blended with
1 kg of fluid described in file Blackoil.mfl. The models and associated
information for the blend are set the same as those in file Blackoil.mfl.

Once the blend is defined as the current fluid, the properties of the blend can be
modified just like any other Multiflash fluid, and the fluid definition can be
saved at any time. If suitable information is available about the properties of the
blend, the model can be modified by fitting to this information using the
Multiflash match utilities.
Example for blending

The case below uses two standard Multiflash examples of petroleum fluid
models defined in Petfluid.mfl and Blackoil.mfl. The first is an oil for which a
PVT analysis is provided and which is characterised by 5 pseudocomponents.
The second is an oil for which no analysis exists, the properties of which have
been estimated by the Multiflash black-oil input option. The second case is
characterised by 15 pseudocomponents, so the two cases are sufficiently
different to present a demanding test of the blending procedure.
Start by loading file Petfluid.mfl using the menu option File/Load Problem Setup
option. Click the phase envelope button and press VLE Autoplot. The phase
envelope appears (after you select continue twice). By default Multiflash adds to
a legend for each phase generated. The legend can be changed using Options in
the bottom of the graph window, e.g. adding the mfl file name for the fluids
before blending.
Without clearing anything, go back to menu option File/Load Problem Setup to
load file Blackoil.mfl. Repeat the VLE Autoplot again using Continue. Both
phase envelopes are now visible on the same plot as shown:

Now the blending procedure can be set up using the blend facility to blend the
two fluids. Without deleting the phase envelopes, press the blend button in the
main Multiflash window and select both fluids using the browse buttons if
desired. Start by mixing 0.25 moles of Petfluid.mfl into 0.75 moles of
Blackoil.mfl as illustrated:
The model definitions used in Blackoil.mfl are selected as the ones to be used for
the blended fluid. On pressing OK, the blending procedure creates a model for
the fluid blend in Multiflash. The phase envelope for the blend can then be added
to the existing plots using VLE Autoplot. The procedure can then be repeated by
going back to the Blend Fluids window and specifying ).5 moles of both oils,
pressing OK and calculating the phase envelope. Finally the process can be
repeated with 0.75 moles of Petfluid.mfl and 0.25 moles of Blackoil.mfl. The
resulting diagram will appear as shown:

As expected, the phase envelopes of the blends move between the two outlying
envelopes of the original fluids depending on the blending proportions.
Example with waxy crudes

The next case involves two standard examples of waxy crudes defined in
waxycondensate.mfl and waxycrude.mfl. The first is a condensate crude with an
n-paraffin distribution estimated from the total wax content; the second has a
measured n-paraffin distribution. The second is much heavier and waxier as its
n-paraffin number goes to much higher molecular weights termination at nC80+
as opposed to nC62+.
First load waxycondensate.mfl and use the VLE Autoplot button on the phase
envelope window to plot the fluid phase envelope. On the phase tab select the
wax phase and press the Plot button to obtain the wax line. The result is as
shown below. (The pressure axis is limited to 450 atm. This is done by selecting
the Frame tab in the phase envelope window and entering 450 in the maximum
pressure box for plotting.). Note that the phase envelope calculations are time
consuming because these examples have a very large number of components.
Next the same calculations are repeated for waxycrude.mfl and the results to
give the following phase diagram. The wax line occurs at a higher temperature
for waxycrude.mfl because the fluid contains heavier n-paraffin components.

Now the two crudes can be blended together using the blending procedure. To
illustrate, the following plot shows a mixture of 0.25 mole for the
waxycondensate.mfl and 0.75 mole for waxycrude.mfl with the final model set
to that of waxycrude.mfl, although it does not matter which fluid definition is
used as the models for both are the same.
As expected, the vapour-liquid phase envelope for the blended crude has mixed
effects from both crudes. The waxy oil is much heavier and has much stronger
effect on the phase envelope of the blended crude at the higher temperature end,
whereas the waxy condensate has more contribution to lower temperature end.
However, the blended wax line is very similar to that of waxycrude.mfl because
the heavier n-paraffins in waxycrude.mfl continue to dominate the point of wax
precipitation in the blended mixture.
Example with asphaltenic crudes

In this example two asphaltenic crudes asphex2.mfl and asphex3.mfl are used.
First, asphex2.mfl is loaded and the bubble point line is plotted by clicking the
Plot button in the phase envelope form. The asphaltene envelope is added by
selecting the asphaltene phase and plotting it from 8500 psia downwards.

The result is characteristic of an asphaltenic oil where asphaltene precipitation
occurs when the temperature falls below the plotted asphaltene boundary.
Next, the asphaltenic crude asphex3.mfl is loaded and the bubble point line is
plotted. The asphaltene line is then selected and plotted from 150 bar upwards.
Finally 0.5 moles of both oils are blended together with the model definition
obtained from the asphex2.mfl fluid. The bubblepoint line and asphaltene
envelope of the blended mixture are plotted. The result is shown below. The
bubble point line is intermediate between those of the two original oils. The
properties of the resins and asphaltenes in the blend is calculated from those of
the original oils using simple averaging rules; in this case the predicted
asphaltene line of the blend is closer to that of asphex2.mfl. The predicted
behaviour is highly speculative as there are no data in the public domain which
can be used to support any model for the blending of asphaltenic crudes. So for
engineering calculations the predictions must be treated with caution.
For the details on how to plot the bubblepoint line and asphaltene envelopes,
refer to the Asphaltenes case study chapter.

Input conditions
Introduction
Once you have chosen the model for your mixture and selected the components,
the next step is to specify the input conditions for the problem. In Multiflash
these may be:
 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. Input
conditions may be specified in a wide range of units; for information on how to
change the units see “Changing units” on page 170. The units currently selected
are displayed next to each input field.
As you may wish to change the input conditions frequently, the majority are
grouped together in the Conditions section of the main window.
If input conditions are defined in a problem setup file they will be displayed
when the file is loaded.
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 Lab
Analysis” on page 89) or to enter the composition of an inhibitor through the
Inhibitor Calculator (see “Inhibitor calculator” on page 79).
To specify the amount of any component in a mixture using the drop down table
under Compositions activate the table by clicking on the Compositions button.
User Guide for Multiflash for Windows Input conditions  137

The table lists the selected components and the compositions should be entered
in the right-hand column, in the units shown. If the composition has been defined
in a 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 total
amounts in either molar or mass units. There is no requirement that they sum to
one or any other value. If you wish to enter mole fractions then the units should
be set to mole, and you must ensure that the values sum to one. Otherwise they
will be totalled in moles and the fractions scaled accordingly. To enter mass
fractions select a mass unit for amounts, eg. g, and enter values that sum to one.
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 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 non-zero amount for at least one component in a mixture for
any calculation to proceed, 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 be warned
when activating a flash calculation,
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
Note that you can copy the composition of a phase from the results window and
paste this into the Composition table to carry out further calculations.
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.
138  Input conditions User Guide for Multiflash for Windows

The numerical value for the temperature, pressure or volume should be entered
in the appropriate text box, in the units shown. If the quantity has been set in a
problem setup file it will be displayed.
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 value is
unacceptable, eg. a negative absolute temperature, you will be asked to re-enter
the value.
If you fail to enter temperature, pressure or volume and this is required for the
flash calculation chosen then a warning will be given. For example, if you try to
carry out 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.
Enthalpy, entropy and internal energy are defined relative to an arbitrary zero
point or datum (see below). Consequently they can take both positive and
negative values and, therefore, there is no check on the value entered. 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.
The default datum points for enthalpy and entropy set the value of both to zero in
the perfect gas state at 298.15K and 1 bar for each compound. Multiflash
provides other choices for the datum points which can be set in the units tab for
the property. The enthalpy datum may be set as compounds or elements and for
entropy there is a further choice of standard. Compounds corresponds to the
default described above. The other settings might be useful in the context of
chemical reactions. More complete descriptions of how these properties are
defined is given in the sections Enthalpy definition on page 178 and Entropy
definition on page 180.
As with temperature, pressure and volume if you fail to set an input value for any
of these quantities 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 are fixed quantities 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 may not be reported as an error in Multiflash.
User Guide for Multiflash for Windows Input conditions  139

Calculations
Introduction
The calculations available in Multiflash may be divided into two broad
categories. Firstly there are simple flash calculations where two quantities such
as pressure and temperature are specified and the amounts and compositions of
all phases at equilibrium are calculated. Other calculation options such as the
Phase Envelope or Reid Vapour Pressure depend on a sequence of flashes to
follow a phase boundary or to simulate a laboratory procedure.
Before carrying out any calculation you must specify the components,
compositions and model(s). The other input conditions appropriate to the
calculation must also be set. For example, the pressure and temperature for a PT
flash. After you have performed a calculation any of the input conditions can be
changed and further calculations carried out.
Most of the calculations in Multiflash work with a single fluid composition and
return a result for a single set of input conditions. If you need to carry out many
calculations and generate tabular output this can be done easily using the
Multiflash Excel interface.. See the separate document User Guide for Multiflash
Excel Interface for details.
The basis of a flash calculation

In a flash calculation the overall composition and any two of the following
variables are fixed:
 Temperature (T)
 Pressure (P)
 Volume (V)
 Enthalpy (H)
 Entropy (S)
 Internal energy (U)
 Amount of a phase
The flash calculation allows you to determine, subject to the constraints imposed
(the two fixed quantities), the number and type of phases present and the
composition and properties of those phases. This is 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
User Guide for Multiflash for Windows Calculations  141

 The pressures of all phases are equal
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 flashIsentropic 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
T, Retrograde dew Upper retrograde dew point at fixed
point 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
All the above flashes may be activated from the Calculate menu and selecting
the flash type and, where appropriate, the particular flash. The flash conditions
are taken from the Conditions section of the main window.
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 carry out an isothermal flash for a given mixture:
142  Calculations User Guide for Multiflash for Windows

Ensure you have chosen a model
Enter the temperature and pressure in the Conditions section
Click on the tool bar button , or, alternatively, choose P,T, Flash from the
Standard Flashes list in the Calculate menu.
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
sequence is:
Determine the enthalpy of a stream at a given P,T (isothermal flash) and 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 also plot lines of constant enthalpy on a phase diagram. See the
description on page 148.
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. Like the P,H flash the P,S flash has a unique solution. 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 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 also plot lines of constant entropy on a phase diagram. See the
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. Both of
these flash specifications have unique solutions. Neither of these flashes has a
tool bar button assigned, both are activated only through Calculate in the Menu
bar.
You can also plot lines of constant volume on a phase diagram. See the
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. In a multiphase situation it is possible to have more than
one dew point (you will probably have more than one liquid phase). The dew
point calculation will return the primary normal dew point, ie. the temperature
(at fixed pressure) at which the first liquid phase appears as the temperature is
reduced or the lowest pressure at which a liquid phase appears (at fixed
temperature).

In most oil and gas systems there is also a retrograde dew point corresponding to
retrograde condensation or condensation of liquid from a gas phase as the
pressure is reduced. The retrograde dew point pressure (at fixed temperature) is
the pressure at which a liquid phase appears as the pressure is reduced
Dew point calculations can be activated from the Calculate menu or toolbar
buttons: and for normal dew points and for retrograde dew points.
Dew point calculations are particular applications of a fixed phase fraction flash
(see below). Dew points corresponding to the appearance of each liquid phase
can be calculated with the fixed phase fraction flash by specifying the name of
the phase and setting the fixed amount of the phase to zero. A common
application is to calculate both the hydrocarbon liquid dew point and water dew
point in oil and gas systems.
The bubble point is the first point at which gas appears as the pressure is reduced
at fixed temperature or the temperature is increased at fixed pressure.
Bubble point calculations can be activated from the Calculate menu or toolbar
buttons: and .
Depending on the temperature or pressure specified and where this is in relation
to the phase envelope and critical point it is possible that a dew point or bubble
point calculation does not have a solution.
Fixed phase fraction flashes

This is 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.
The Fixed Phase Fraction Flash (FPFF) is a generalisation of the dew and bubble
point calculations described above.
Phases
Multiflash is a multiphase phase equilibrium program that can handle up to
twenty possible 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
 Pure solid
 Fixed composition 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 312. The standard set of names used
for the different phases is listed below.
Phase names
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.
Fixed composition phases are included for the halide scales: NaCl, NaCl.2H2O,
KCl, CaCl2.2H2O, CaCl2.4H2O, CaCl2.6H2O, NaBr, NaBr.2H2O, KBr and
CaBr2.6H2O.
It is possible to create phases with any name, not just the standard list shown
above. If you load a problem setup file that was not created in the Multiflash
GUI you may see other names.
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.
A supercritical phases (often termed ‘dense phase’) represented by equation of
state models cannot be assigned an unambiguous phase type. In other words
there is no way to distinguish between a gas phase and a liquid phase. The rule
used in Multiflash is that a supercritical phase is labelled as GAS if VT2 > VcTc2,
where Vc is the pseudo critical volume and Tc is the pseudo-critical temperature.
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. Alternatively a minimum key component can
be specified; this means that the component should be present in the phase in the
minimum relative concentration.
Since version Multiflash 4.4, multiple key components can be specified for the
phases.
The phases set up by the Multiflash GUI identify one liquid phase (WATER)
with aqueous components as key components as the key component and the
other two liquid phases (LIQUID1 and LIQUID2) with aqueous components as a
minimum key component. The aqueous key components are the mostly used
polar components such water, methanol, ethanol, glycols, etc.
Key components are only needed when a flash calculation must identify a phase
uniquely (e.g. search for a particular phase fraction). Examples are the fixed
phase fraction flash or a phase envelope calculation.
If you request any of these calculations for a phase without a specified key
component, an error message will be returned. For example, if you try to
calculate the water dew point when there is no water in the mixture you will see
the following message:
*** ERROR 20148 ***
Key components of fixed phase not present or in
trace amounts.
*** ERROR 21011 ***
Illegal input specification

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 fixed phase 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 at least one key component
for one of two non-aqueous liquids. To do this it is necessary to use the
Command window from the Tools menu. See ‘Defining phase descriptors and
key components’ on page 314. See also the command reference manual.
For example the following command will set heptane as the key component
(present in highest concentration) for the phase liquid1.
keys liquid1 heptane;
Another possibility is to use the following specifications for selecting the lightest
and heaviest liquid phases:
keys liquid1 heaviest;
keys 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 and
hence the phase labelling can change even though there is no actual phase
change.
Using the fixed phase flash

To use the fixed phase flash either click on the fixed phase flash button for fixed
pressure or fixed temperature or select the option from the Calculate
menu.
The following dialogue box will be displayed.

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.
Enter the fraction of the phase that you want to fix. This fraction must be
between 0 and 1. To search for the temperature or pressure at which the phase
first appears (the phase boundary) set the phase fraction to 0. However you can
also 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 with the Normal (default
solution) option button selected. However, most oil and gas systems exhibit
more complex phase behaviour. A typical phase diagram is shown below.
The critical point is where the gas and liquid phases become identical, having
the same density and composition. It is also possible to have liquid-liquid critical
points where two liquid phases become identical. The cricondentherm is the
maximum temperature at which a two phase mixture can exist and the
cricondenbar is the maximum pressure at which a two phase mixture can exist.
If the pressure is reduced along an isotherm from the liquid or dense gas region
(to the left of the critical point) it reaches its bubble point, where the light
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 is reduced (to the right
of the critical point) the liquids drop out of the gas phase at the retrograde dew
point and the amount of liquid increases as the pressure decreases. This is known
as retrograde. condensation.. As the pressure is reduced further, the liquid
components evaporate again and the liquid disappears at the normal dew point.
For example, consider the phase envelope shown above, which has a large
retrograde region. Taking a temperature of 300oF, for example, there are two
dew points; one at 2.5 psia (the normal dew point) and one at 2977 psia (the
retrograde dew point). The Type of Solution setting allows Multiflash to
calculate either the normal or retrograde solution to a fixed phase fraction flash.

In the special case of the dew point there are dedicated calculation options as
described previously.
The Unspecified setting for the type of solution is sometimes useful when
dealing with complex phase behaviour that does may be quite different from the
familiar Vapour + liquid situation discussed above. The Unspecified setting will
cause Multiflash to search for the nearest solution to its starting point without
any distinction between normal and retrograde behaviour. One example of where
Unspecified may be needed is when calculating an asphaltene phase boundary
above the bubble 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.
Phase Envelopes
The Phase Envelope utility will trace any phase boundary including gas, liquid
and solid on pressure-temperature co-ordinates. The phase envelope utility will
work with any Multiflash model but some models, such as activity coefficient
models, are only valid at low pressures and will not produce closed phase
boundaries.
Other features include:
 the ability to trace selected phase boundaries on the basis of mass
or volume fraction in addition to mole fraction and the nucleation
boundary.
 the flexibility to include the plotting of constant enthalpy, entropy,
volume or free energy boundaries.
 A generalisation of the plotting facility so that for any chosen
phase boundary it is possible to plot any phase or property against
another.
The use the Phase Envelope utility click on the Phase Envelope toolbar button,
or select the option from the Calculate menu.

A window similar to the following is displayed:

The buttons along the bottom of this window perform calculations or other
actions the three tabs that control what is calculated and plotted.
VLEAutoPlot
The VLEAutoPlot button will generate a vapour-liquid phase boundary starting
from the dew point line at low pressure. This is the usual phase envelope
calculation. None of the settings on the Phase tab or Initial Values tab are used
by this option.
It is possible that the message box shown below will be displayed
The default for the maximum number of points to calculate is 100. This may not
be sufficient to complete the phase boundary. Clicking on Yes will allow the
calculations and plot to continue. If the calculations have reached any limit
within the 100 points the message will not appear.
Phase tab
The Type of Solution, Select Phase, Select Basis and Phase Fraction boxes are
used when you click on the Plot button.
The Select Phase box allows you to select the specific phase for which you wish
to plot a boundary, for example WATER. The Phase Fraction box sets the value
of fraction of the phase selected to be plotted. For example, to plot the water dew
point line select the WATER phase and set the phase fraction to 0 and click on
Plot. A phase fraction of zero should always be used to plot the boundary where
a phase first appears (or disappears). Phase fractions greater than zero will plot
lines where the selected phase is present with the fraction specified. As with the
dew, bubble and fixed phase fraction calculations there may not be a solution for

the specification made. For example, if the phase fraction of the water phase is
set as 1.0 it is unlikely that there will be a solution unless the composition is
almost pure water.
The Type of Solution settings have the same meaning as discussed previously.
Normal should usually be selected.
The Select Basis box allows you to select the property to be plotted.
The mole fraction, mass fraction and volume fraction properties refer to the
fraction of the specified phase. To calculate a phase appearance boundary (with a
fraction of 0) it is recommended that you select the mole fraction basis.
Selecting enthalpy, entropy, volume or internal energy will disable the Type of
Solution and Select phase boxes because the property line plotted is the total for
all the phases present. The value of the property to be plotted should be entered
in the units shown. The units can be changed by clicking on the Units button.
Click the Plot button to plot the constant property line.

Initial Values Tab
The settings on the Initial Values Tab are used when the Plot button is clicked.
They are disregarded for the VLEAutoplot operation.
The Initial Values section allows you to set a pressure or temperature value for
the start of the phase boundary or property plot.. The Start from setting selects
either the pressure or temperature as the starting point and the Initial value to
section sets the initial direction for the pressure or temperature.
Pressure increasing from 1 bar is the default setting and is usually a good choice
for many phase boundaries. However, you should be aware that occasionally
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.
When plotting phase boundaries for solids it is often a good strategy to start from
a high pressure and change the direction to decrease.

If the boundary still proves difficult to trace, starting values for both the
temperature and pressure can be provided. Checking the Use starting value box
will then provide Multiflash with an initial guess for the starting point and may
make it possible to trace the phase boundary.
Frame Tab
The Frame tab 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 axes.
The section headed For Calculation allows setting of minimum and maximum
values for temperature and pressure that will be used when calculating a phase
boundary or property line. It is usually best not to enter any limits because the
ranges for the calculation are usually unknown in advance. If the initial point on
a line falls outside the specified range no further calculations will be done.
The For Plotting section controls how the results of the calculation are
displayed. Normally the x-axis displays temperature and the y-axis displays
pressure. However these settings can be changed to enthalpy, entropy, volume,
internal energy or the fraction of any phase. All the possibilities are shown in the
drop-down list for each axis. The minimum and maximum values for plotting on
each axis can also be set. If the T,P range for calculation is limited then the
plotted values will also be limited irrespective of the plotting range set.

A typical phase envelope plot might be a VLE plot for a hydrocarbon fluid. The
axes will be pressure versus temperature.
By changing the plotting variables 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 also allows you to change the maximum number of points
calculated at any one time. A limit is needed because some phase boundaries do
not have a natural end point or form closed loops. The default value for the
maximum is 100. This limit can be increased if desired.
Phase Envelope Output

A typical phase envelope output is shown below. The boundary labelled V/L=0
is generated with the VLEAutoPlot function. The other phase boundaries are
added one at a time with the Plot function.

Any critical points are labelled with a C and discontinuities, where phase
boundaries cross, are marked with a D.
The numerical values for each point plotted are displayed in the main window.
Critical points or discontinuities are marked with a C or D in the table.
Phase envelope output:
T/K P/bar
39 294.300 110.80
40D 294.300 110.80
41 294.304 110.95
42 294.306 111.03
The first column is the number of the point plotted.
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.
Options
The Options button allows you to delete or customise each line on the plot.
You can change the label, the colour and line style. Tool bar buttons on the plot
window also give access to the controls of the graphics package. The Edit button
provides detailed adjustments.

Add Data
The Add Data button allows you to add data points to the plot. These would
typically be experimental points that you wish to compare with predictions.
Clicking on Add Data displays a table.
Enter the data to be plotted (which can be pasted) and click on Save and Plot.
Several data series can be added.
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 generated in the Multiflash GUI 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 onwards.

PT flash
It is possible to do a PT flash at any point on the phase diagram plot. Moving the
cursor across the plot displays the temperature and pressure as X, Y coordinates
above the plot.
Right-clicking the mouse displays the PT Flash button. Click on this button to
carry out a PT flash at the conditions shown. The output is displayed in the main
window.
Phase Envelopes for solids

The phase envelopes for solids button, is designed to make it easier to
generate all the fluid and solid phase boundaries simultaneously by just clicking
the button. The phase boundaries plotted depend on the models and phases
currently defined. If there are no solid phases present, only the V/L phase
envelope will be plotted. A PT flash can be carried out by right clicking with the
mouse as described above.
The following plot shows an example including hydrates, ice, water, liquid
hydrocarbon and vapour phases.

The next example shows a complex phase diagram including hydrate, ice, wax
and asphaltene phases together with the usual vapour, hydrocarbon liquid and
water phases.
Liquid dropout curve calculation

Liquid dropout curves are routinely measured by PVT Laboratories as part of a
constant mass expansion experiment on condensates. The liquid dropout is
defined as the volume percentage of the hydrocarbon liquid phase at a given
pressure relative to the total volume of the mixture at the upper retrograde
dewpoint. The experiment is carried out at a fixed temperature.
To calculate a liquid dropout curve choose the option from the Calculate menu
or click on the toolbar button
A typical example of liquid dropout curves at two different temperatures is
shown below.
It is possible that an upper retrograde dewpoint is not found at the given

temperature, ie. the condition is on the bubblepoint side of the critical point. In
such cases the volume of the liquid phase is calculated relative to the total fluid
volume at the saturation point (bubble point) at the given temperature. An
example is shown below.

Hydrate calculations
All the flash calculations in Multiflash can include solid phases such as hydrates.
The hydrate dissociation temperature or pressure can be calculated using the
Fixed Phase Fraction Flash. However, since there is a possibility of up to three
hydrate phases (with different structures), specific calculation options for
hydrates are provided to simplify the task.
To calculate the hydrate dissociation temperature at fixed pressure or hydrate
dissociation pressure at fixed temperature select the Hydrates option from the
Calculate menu or click on the appropriate toolbar button: or . The
flash will return the temperature or pressure at which a hydrate phase is present
in zero amount (the dissociation point). The hydrate structure and all the phase
properties are also displayed.
For more information on calculations with hydrate see the section Case studies -
Hydrate dissociation, formation and inhibition on page 243 .
Wax calculations
As with other solids, a wax phase can be included in any flash calculation in
Multiflash. In addition there are two dedicated calculations involving wax.
Wax Appearance Temperature

The wax appearance temperature (WAT) is the temperature at which a small
amount of wax phase appears as the mixture is cooled at a specified pressure. An
experimental measurement of the WAT requires a detectable, non-zero, amount
of wax to be formed. However, the calculation of the WAT is very sensitive to
small amounts of heavy alkanes in the mixture so very different WAT values can
be obtained depending on the criteria for detectability. The two most common
experimental techniques are Cross Polar Microscopy (CPM) and Differential
Scanning Calorimetry (DSC). The CPM technique is more sensitive than DSC
and, in general, detects the presence of a smaller amount of wax. Hence the
WAT measured by CPM will usually be higher than the measurement by DSC.
After reviewing the WAT measurements in our database we have developed
guidelines for detectability limits for the two techniques and these are included
in the WAT calculator.
To do a WAT calculation click on the toolbar button or select the Wax

option from the Calculate menu. The following window is displayed.

For CPM we suggest a criterion of 0.045 mass percent wax as the detectability
limit and for DSC the suggested value is 0.3 mass percent. It must be emphasised
that these figures are guidelines and may not apply in all cases.
Clicking the Calculate WAT button will calculate the temperature
corresponding to the wax percentage specified at the pressure set in the input
conditions.
Wax Precipitation Curve

The wax precipitation curve option calculates the amount of wax precipitated as
a percentage of the wax plus oil phases as a function of temperature.
Measurements of the amount of wax formed as a function of temperature are, in
general, more reliable than WAT measurements which, by definition, are at the
measurement limit.
To calculate a wax precipitation curve click on the toolbar button or select

the Wax option from the Calculate menu. A window similar to the following is
displayed
Enter the pressure for the calculation in the pressure box and click Calculate. The
curve is displayed in the plot window and a table of values is shown in the
Multiflash output window
Wax Precipitation Curve
Pressure: 1. bar
T (degC) Wax mass percent in liquid(+wax)

0. 5.12253
4. 4.52423
8. 3.89114
12. 3.23714
16. 2.57435
20. 1.93908
24. 1.40141
28. 1.00565

32. 0.725042
36. 0.525915
40. 0.377582
44. 0.271559
48. 0.195085
52. 0.131349
56. 0.0696203
60. 0.0172402
64. 0.00132507
66.40 0.
The starting temperature is 0°C, or the equivalent in other units, and the finishing
temperature is the calculated WAT for zero % wax. The maximum number of
points is twenty but the actual number of points will depend on the WAT, the
units used and the step size.
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 fixed phase 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 opens the following window
In the Phase Specified tab window set the phase and the fraction of that phase
for the fixed phase element of the flash. In the Composition of Second Fluid tab
enter the amount of the single component (usually 1.0) or the composition of the
mixture to be added to the main stream to meet the phase fraction 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, ie. to prevent hydrate
formation at the given conditions..
Reid Vapour Pressure

The Reid vapour pressure (RVP) is usually employed by refineries to quantify
and modify the vaporization of gasolines and other volatile petroleum products.
RVP is a measure of the volatility of a fluid; it is reported as the gauge pressure
of a unit volume of the petroleum fluid in equilibrium with 4 unit volumes of air
at 100 °F (37.8 °C). The Reid vapour pressure of a fluid is different from its true
vapour pressure, as it is calculated considering air as part of the fluid
composition.
Reid vapour pressures are obtained experimentally according to the ASTM-D-
323 test method. This standard is for volatile crude oils and volatile non-viscous
petroleum liquids and it excludes liquefied petroleum gases.
To calculate the RVP of a mixture select Reid Vapour Pressure from the
Calculate menu.
The calculation mimics the experimental procedure, as described in the ASTM-
D-323 method. This standard requires that the mixture is one phase liquid or
liquid + vapour at the simulated experimental conditions. Water should not be
present in the mixture. Other phase behaviour, such as multiple liquid or solid
phases are not allowed by the experimental method and Multiflash will generate
and an error message
No liquid phase or multiple condensed phases were
found at the flash conditions
Another error message will be shown if the fluid is not sufficiently volatile to be
considered a volatile petroleum product:

Negative Reid Vapour pressure obtained. Mixture
pressure is lower than 1 atm
Reid vapour pressure calculations can be done with both real components and
petroleum fractions using any appropriate thermodynamic model. However,
special care is recommended when selecting the model for the calculation. While
for most of the standard volatile fuels any cubic equation of state can be selected,
when dealing with oxygenated fuels, such as mixtures with ethanol, the CPA
Infochem model should be used to ensure that the correct phase behaviour is
predicted.
The following example uses a mixture of 93.57 mol % isopentane and 6.43 mol
% ETBE (ethyl tert-butyl ether) (file ReidVP_ex1.mfl). The reported
experimental Reid vapour pressure is 19.1 psi. Using the RKSA model s
calculated value of 18.8 psi is obtained.
Note that this example assumes that you have a DIPPR databank license this is
because ETBE is not available in Infodata databank and must be defined from
the DIPPR databank.
If you do not have a DIPPR license, the example ReidVP_ex2.mfl can be used
instead. This is a mixture of different gasoline components (in the range C5-C7)
and ethanol. As ethanol is part of the mixture, the CPA model should be used to
ensure realistic predictions (the RKSA model will wrongly predict liquid-liquid
phase splitting).

The calculated value is now 10.8 psi. A low volatility gasoline will have a Reid
vapour pressure around 6 psi, while a high volatility gasoline will be in the range
of 15 psi. The example presented thus corresponds to a hypothetical gasoline of
intermediate Reid vapour pressure
Property output in Multiflash

Multiflash provides several levels of physical property output following a flash
calculation. The default is to list the phases present , with their amounts,
compositions, thermal and volumetric properties. It is possible to get more
output such as heat capacities and compressibility and fugacity and activity
coefficients for each component in each phase. You can also calculate and
display diffusivity provided you have checked the “include diffusivity
coefficient” box when defining the model set. 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 menu option. The
following dialogue box will be displayed

You can also trigger the same dialogue box using Tools/Preferences to set your
preferred level of property output as the default.
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 plus the
transport properties. The later will be omitted if no transport models are defined
To reduce the amount of output deselect any properties not of interest. If you
choose Heat Capacity and Speed of Sound etc. the phase amounts and
composition plus the volume and thermal property output are also automatically
selected. Examples of the property output options are shown in “Calculation
output” on page 175.
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.
Some flash calculations gave a unique solution. These include (P,T), (P,H),
(P,S), (T,V), (U,V) and (S,V). In principle, these flash calculations should
always have a solution. However, in practise, the range of conditions for which a
solution can be found depends on the models used. For example, if the volume
specified for a flash is smaller than the b parameter for a cubic equation of state
it is not possible to solve any flash that includes the volume.
Dew and bubble point calculations (and fixed phase fraction flashes in general)
are common cases of flashes that may have no solution, a single solution or
multiple solutions. When one of these calculations fails it will produce output
similar to the following in the main output window
Bubble 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

The phase envelope plotter is a convenient way to determine 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 Envelopes” on page 148.
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.

You can use a right click in a phase envelope plot to carry out a PT flash
anywhere on the plot. See the description on page 157.
Limit the number of phases

Multiflash is designed to consider the possibility of all the phases specified in the
Model Set being formed and to establish the most stable solution. The model sets
for 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 a retrograde solution.
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 useful for any
flash other than the PT flash where both quantities are already specified.
From the Select menu click on Use Starting Values.

Carry out the flash calculation. The temperature or/and pressure (as appropriate
for the flash calculation) set in the input conditions text box will be used as the
starting value for the calculation.
To turn off the use of starting values, use the Select menu again and click to
remove the check mark by Use Starting Values .
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 estimates of the composition.
Provide a key component

As we have discussed earlier, “Key components” on page 145,. 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.

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. Unless altered by the user, the default input and output units are also SI
and any numerical input values for any property will be assumed to be in SI.
The input values of component 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 each phase is the total amount.
Default units
In the absence of any other information the default input and output units are
also SI. However, if you prefer to work in other units most of the time it is
possible to set these as your preferred option. This is done through the Tools
menu by selecting the Preferences/General option.
Under the Default Units tab select your choice of units for any property. In the
example below the default unit for pressure is set to bar rather than Pa.
User Guide for Multiflash for Windows Units  169

If you exit Multiflash and re-launch the software the pressure units will
automatically be set to bar.
However, you should be aware that if you load an .mfl file where you had
included numeric values for pressures, but not specified the units, these will now
be assumed to be in bar. This problem can only arise if you create your own .mlf
files using a text editor rather than using the Multiflash GUI.
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. As
with any other units these defaults can be changed.
Changing units
You may change any of the input or output units at any time. This does not affect
the default unit settings described above.
From the Select menu choose Units or click on the Select input and output units
toolbar button . This displays the Unit Selection window:
170  Units User Guide for Multiflash for Windows

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. Do the same in the Output unit
column to change the output units for that property. The input and output units
may be different.
The units for output (calculated) composition may be changed from fractions to
total amounts on the Amounts tab. It is not possible to change the input
composition to fractions.
The Unit Selection window 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, Matching options, Tables etc.
Units can be also 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
All British;
lbmol, DegF, psi, ft3/lbmol, BTU/lbmol, BTU/lbmol/F, cP, BTU/hr/ft/F,
dyne/cm, cm2/s
If you save a problem setup the unit definition will also be saved as part of the
problem setup file.
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  171

Output
Introduction
The numerical 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 174.
The results window

As soon as Multiflash opens the banner appears in the results window.
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 of the Multiflash application files location. It also shows
the contents of the MFCONFIG.DAT file if you have one. The path for the
location of the Multiflash log file can be found from the “About Multiflash …”
under the Help menu of the Multiflash main window.
When a problem setup file (.mfl file) is loaded the contents of the 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 identify the calculation. For example
Dew point at fixed T:
A confirmation message may be displayed be certain menu options. For
example, the Clear Problem Setup option in the File menu shows the following
message to confirm that the previous setup has been removed
Clear current problem setup
User Guide for Multiflash for Windows Output  173

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 300kb of text 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 exceed 300kb.
If some of 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 through the Tools menu by selecting the
Preferences/General option and the Sheet Configuration tab and clicking on
the Fonts button.
The possible fonts available will depend on the particular PC installation. When
changing fonts we recommend that you always choose a mono-spaced font so
that the column format is retained.
Writing the results to a file

As well as being displayed in the results window the output is also sent to a log
file which may be examined later. The log file is called MFLASH.LOG. Each
time Multiflash runs the previous log files are renamed sequentially as
MFLASH_1.LOG, MFLASH_2.LOG up to MFLASH_10.LOG. This allows you
to refer back to earlier Multiflash sessions. The oldest file MFLASH_10,LOG is
deleted when a new Multiflash session is started. If you wish to keep any of the
log files you should rename them.
You can also save all the output to a file at any time using the Save Results
option from the File menu. A confirmation message is displayed
174  Output User Guide for Multiflash for Windows

If you have previously selected part of the output the following message is
displayed.
A file save dialogue allows you to choose the file name and folder. The default
extension for output files is .out, but you may choose any extension that is
allowed by Windows.
Printing the output

You can print the output from your calculations by selecting the Print Results
option from the File menu or clicking on the toolbar 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 will 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 will 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 or solid cannot be already defined. The results of a hydrate nucleation calculation will always be
checked labelled unstable because it is not an equilibrium point. 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). If molar output units are selected for amounts (default) the
compositions shown are mole fractions, but the total amount of each phase is in
molar units. 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. ‘Den/V’ 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
Sp.Sound (m/s) thermodynamic speed of sound
Compress (1/bar) the compressibility
Expansiv (1/K) the expansivity
JT (K/bar) the Joule-Thomson coefficient
Visc.(Pas ) viscosity
Th.C.(W/m/K ) thermal conductivity
STen (N/m) surface tension
The format for the surface tension output depends on the surface tension model
selected. For the Macleod-Sugden model (MCS) there is an entry for each liquid
phase. This is the liquid-gas interfacial tension. For the linear gradient theory
model (LGST) the interfacial tension between each pair of phases is displayed in
a grid. This will include liquid-liquid interfacial tension as well as the liquid-gas
values.
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 numeric 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
Manipulating the Output

As described above the appearance of the output can be configured to your
liking. Font type, size and colour can be altered as can the background of the
results window. Gridlines can be added to clearly distinguish between columns.
You can copy any proportion of a column and paste this directly into another
grid. The composition of a liquid from a flash can be copied and directly pasted
to the input composition table. The amount of a second phase to be added to the
overall stream composition from a tolerance calculation can be copied and added
to the Composition table.

Phase Labelling
The list of phases displayed after a flash calculation shows the phase label for
each phase. At low pressures there is usually a clear distinction between a gas
phase and a liquid phase. This is no longer the case in the ‘dense phase’ region
above the vapour-liquid phase envelope where the phase present is supercritical.
In such cases there is no physical distinction between a gas and a liquid. The
phase label assigned by Multiflash is arbitrary.
The criterion used to decide whether to call a supercritical phase gas or liquid is
as follows.
 A phase is labelled as gas if VT 2  Vc Tc2 where Tc and Vc are

the pseudo-critical temperature and volume.
 Otherwise the phase is labelled as liquid.
 The pseudo-critical properties are model-dependent and do not
correspond to the true critical properties for a mixture.
These conditions only apply to equation of state type models that can represent
both gas and liquid phases. The phase properties such as density, enthalpy etc.
are not affected by the label attached to the phase since, by definition, the phase
is supercritical and there is only one solution for the volume of the equation of
state model.
Aqueous phase labelling

The aqueous phase labelling in the current version of Multiflash has changed. In
previous versions only one key component was used, but now it is possible to
define multiple key components. For version 4.4 onwards, the water phase is
assigned a new special keyword “AQUEOUS”. This means that the following
list of components will be used as water key components:
 water
 methanol
 ethanol
 MEG
 DEG
 TEG
 Glycol
 Propylene glycol
 Propylene glycol monomethyl ether
 dipropylene glycol
 dipropylene glycol monomethyl ether
The non-aqueous phases are assigned also a new keyword as key component:
“*”.The “*” keyword is used to denote a phase which has negligible amounts of
the positive key components of all the other phase descriptors.
This is now the default behaviour when using the Graphical User Interface.
Enthalpy definition
In Multiflash the enthalpy is calculated as

H  H ref  H pg  H res
Where:
H ref is the (arbitrary) enthalpy value in a reference state to be defined;
H pg is the perfect gas contribution to the enthalpy which is calculated by

integrating the equation for the perfect gas heat capacity;
H res is the residual enthalpy which is calculated from the thermodynamic

model specified for thermal properties.
The absolute value of enthalpy has no physical meaning but enthalpy differences
are measurable quantities therefore H ref can be chosen at will. Multiflash has
two possible reference states that are user selectable. By default we set to zero
the enthalpy of each pure component in the perfect gas state at 298.15K and 1
atm. This reference state (or datum) is referred to as the ‘compound’ datum in
the units selection window of Multiflash. See “Units” on page 169.
An alternative datum in Multiflash (the ‘elements’ datum) sets the enthalpy of
each element to zero in the perfect gas state at 298.15K and 1 atm. This datum
produces enthalpy values that are much larger numerically than the ‘compound’
datum but enthalpy differences between two states are the same. When
calculating chemical reaction equilibrium the ‘elements’ datum must be used
because it is the elemental entities that are conserved rather than the molecular
entities. If you observe differences in enthalpy values calculated with Multiflash
and other software this is likely to be because of different choices of datum.
However, enthalpy differences should not be very different.
Activity Models
For activity methods the default route for calculating the enthalpy is as described
above. However, there are two additional routes by which the enthalpy of each
component can be calculated. Although the alternatives described below are
available, it is recommended that they should only be used if the consequences
and implications are well-understood.
Liquid enthalpy based on saturated liquid heat capacity

The data stored for each pure component will normally include a correlation for
the saturated liquid heat capacity (Cp) as a function of temperature. The enthalpy
can be calculated based on the liquid Cp correlation instead of the perfect gas Cp
correlation as usual.
With this option for the liquid phase the pure component enthalpy at the
reference state, 298.15K and 1 atm is calculated with the existing procedure
described above. Then the total enthalpy of pure components at the system
temperature is calculated by adding the integral of the liquid C p from the
reference temperature to the given temperature plus the enthalpy change on
evaporation at 298.15K, the Poynting correction and the excess enthalpy
calculated from the activity coefficient models.
The enthalpy for the gas phase is calculated by the default method. The
consequence is that that the liquid heat capacity is based on the stored correlation
for the liquid phase so it may be expected to be more accurate than the value
calculated by the default method that is, ultimately, based on the perfect gas heat
capacity. However the enthalpy difference between gas and liquid is no longer
based on the databank correlation for enthalpy change on evaporation.

Gas and liquid Enthalpy based on saturated liquid heat
capacity
With this option the liquid phase enthalpy is calculated as described above. The
gas phase enthalpy is obtained by subtracting the enthalpy change on
evaporation from the liquid phase value.
This procedure provides liquid phase enthalpy and Cp based on the databank
correlation for liquid Cp. The enthalpy difference between gas and liquid is
based on the correlation for the enthalpy change on evaporation. However, the
gas phase enthalpy is no longer based on the perfect gas heat capacity and
would, therefore, be expected to be less accurate than in the default method.
Entropy definition
In Multiflash the entropy is calculated as
S  S ref  S pg  S res
Where:
S ref is the (arbitrary) entropy value in a reference state to be defined;
S pg is the perfect gas contribution to the entropy which is calculated by

integrating the equation for the perfect gas heat capacity;
S res is the residual entropy which is calculated from the thermodynamic model
specified for thermal properties.
Although the absolute entropy can be argued to have a physical interpretation, in
practise, it is entropy differences that are experimentally accessible and S ref can
be chosen at will.
Multiflash has three possible reference states that are user selectable. By default
we set to zero the entropy of each pure component in the perfect gas state at
298.15K and 1 atm. This datum is referred to as the ‘compound’ datum in the
units selection window of Multiflash. See “Units” on page 169.
The ‘elements’ datum sets the entropy of each element to zero in the perfect gas
state at 298.15K and 1 atm. This datum produces values that are much larger
numerically than the ‘compound’ datum but entropy differences between two
states are the same. When calculating chemical reaction equilibrium the
‘elements’ datum must be used.
The third possibility is the ‘standard’ datum which is sometimes called the
‘third-law or ‘absolute’ entropy. This means that the reference entropy is chosen
so that the entropy of each component in the perfect gas state at 298.15K and 1
atm is equal to the standard entropy of that component. The standard entropy is
relative to a zero value at absolute zero. The standard datum may also be used in
chemical reaction analysis since the results are equivalent to the elements datum.
Activity Models
The two alternative calculation routes for the enthalpy have corresponding routes
for the entropy. They always apply to both properties.

Errors and warning messages
Errors are usually associated with Multiflash output indicating a failure to find a
solution or that the results may be invalid. Error messages and warning messages
are displayed in the results window. Each error and warning has a unique
identification number. Errors are denoted by positive numbers and warnings by
negative numbers. The error number is followed by a single line description of
the problem. For example
Dew point at fixed T:
*** 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
When several errors are reported, as above, it is the first error that is closest to
the fundamental problem. For more information on each error code see
Multiflash Error Codes in the Help menu. The information on the module in
which the error occurred and the subprogram name is intended for use by
Infochem technical support.
Warning messages should be checked carefully. In many cases they may be
ignored if the cause is understood.
Displaying status for current settings

Show options in the Tools menu allow the user to check the status of some
Multiflash options. The options are summarised in the following table.
Show options
BIP databank The name of the active BIP bank for the problem e.g.
oilandgas4
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
Results Re-display of the results from the last calculation
Stream Types Displays number and names of active streams
The output from the Show Problem option is essentially identical to the
information written to an .mfl file is the current problem setup is saved.
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 300kb for the results window. If your output
exceeds this then, as the last 300kb 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 164, or
because a model for the property has not been defined.
You should ensure that you have defined transport property models 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. A change in the phase label does not
affect the correctness of the results or phase properties, it is only the label
attached to the phase that is ambiguous.
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 the display.
To change the font setting see “Font” on page 174.

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. In addition,
Multiflash can also import files from other programs (e.g., PVTSim) to perform
calculations. Multiflash can currently produce Pipesim PVT files, files for input
to OLGA, property files for Prosper, and CAPE-OPEN property package files.
Multiflash can also import CHC files from PVTSim.
Pipesim PVT files

Pipesim is a general purpose simulator for modelling fluid flow in oil and gas
wells, flow lines 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, water cut 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 Pipesim from the Table menu, then
Fill in the dialogue box. with the pressure and temperature grid points and the
name of the output file. The recommended file extension is .PVT
User Guide for Multiflash for Windows Interfaces with other programs  183
Click on Calculate table
An alternative to entering each pressure and temperature individually is to use
the Equidistant Points Tab which allows you to enter start and end points for P
and T and an increment or a number of points.
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 written to file: pipe1.pvt
If there are problems calculating any of the entries in the table the following
message is displayed
and more details are reported in the output window.

It should be noted that any BIPs specified by the user in Multiflash will not be
stored in the .pvt file, although numerical values will have been calculated using
them. However, in line with recent changes to PIPESIM .pvt files written with
Multiflash will contain information on the version of the OILANDGAS BIP
correlations and the viscosity model used.
OLGA
OLGA is a general purpose transient simulator for modelling fluid flow in flow
lines and pipeline systems. It is a product licensed by the SPT Group.
Multiflash can produce a PVT data file for use in 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 SPT Technical Note No. 1. From Multiflash
184  Interfaces with other programs User Guide for Multiflash for Windows
4.4, the maximum dimension of the temperature and pressure grid has been
extended up to 100.
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 OLGA from the Table menu, then
Fill in the dialogue box with the pressure and temperature grid points and the
name of the output file. The recognised extension for OLGA tables is .tab. This
will be allocated automatically if you use the Browse facility to identify a
suitable folder and save the file there. Alternatively you can type in the .tab
extension as part of the file name. If you want the file saved in a folder directory
you must enter the full pathname, otherwise the file will be saved in the current
default directory. If the file already exists, the fluid PVT table will be added to
the end of the existing file if the append box is ticked, otherwise the entire file
will be overwritten with the new PVT table.
OLGA requires a File id (starting with a letter not a number). If you don't
provide one, Multiflash will assign one automatically.
Click on Calculate table
If the file already exists and the append box is not ticked, a warning message will
be displayed
Clicking Yes causes the file to be overwritten with the new table. Clicking No
means nothing will happen.
Assuming there are no problems with the calculations 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
Similarly to the Pipesim table option you have the choice of entering the P and T
points for the table or specifying ranges and increments or the number of points.
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 with the message
OLGA hydrate file

In addition to the PVT table, Multiflash can also write an OLGA hydrate file
defining the boundary of the hydrate forming region. This is done by entering a
file name in the hydrate file box or clicking the Browse button. The default
extension for a hydrate file is .hyd. The hydrate file is written at the same time as
the PVT table when the Calculate Table button is clicked. The same style of
warning will appear if an existing hydrate file is about to be overwritten. If the
hydrate file box is left blank, the hydrate calculations are omitted.
If the hydrate file is required but the hydrate model and hydrate phases are not
defined, the following warning is displayed. Choose the Model Set option from
the Select menu to define the hydrate model. It should then be possible to
generate the OLGA hydrate file.
OLGA wax file

Multiflash can also write an OLGA wax file defining paraffin wax precipitation.
This is done by entering a file name in the wax file box or clicking the Browse
button. The default extension for a wax file is .wax. The wax file is written at
the same time as the PVT table when the Calculate Table button is clicked. The
same style of warning will appear if an existing wax file is about to be
overwritten. If the wax file box is left blank, the wax calculations are omitted.
If the wax file is required but the wax model is not defined, the following
warning is displayed. Choose the Model Set option from the Select menu to
define the wax model. It should then be possible to generate the OLGA wax file.
Prosper PVT files

Prosper is a well performance, design and optimisation program for modelling
well configurations for the oil and gas industry. It is a product of Petroleum
Experts.
Multiflash can produce a PVT data file for use by Prosper. The file contains all
the physical property information required by Prosper. It consists of a series of
flash calculations on a grid of temperature and pressure values. For a complete
definition of PVT files please see the Prosper manual.
To generate the file

Define the models (which must include model for viscosity) and the mixture
(components and composition) as usual
From the Table menu choose Prosper. The Prosper PVT Table window is
displayed:
Enter the file name. The recommended file extension is .pvt

The Fluid Id field is an optional identifier that will be written to the file.
You can select the (input) units of temperature and pressure for the table from
the drop-down boxes. Note that the units in the table file are fixed with the
temperature in ºF and the pressure in psig.
Enter the temperature and pressure points for the table. For each isotherm, up to
15 pressures can be specified on the form.
The properties tabulated can be selected using the check-boxes in the Properties
frame. The properties are defined as follows:
Keyword Description Unit
GOR Gas-Oil ratio scf/sbl
OFV Oil formation volume factor RB/sbl
OVIS Oil viscosity cPoise
ODEN Oil density lb/ft3
OCOM Oil compressibility 1/psi
GFVF Gas formation volume factor ft3/scf
GVIS Gas viscosity cPoise
ZFAC Gas Z factor
GDEN Gas density lb/ft3
CGR Reservoir condensate-gas ratio bbl/MMscf
WVIS Water viscosity cPoise
WCOM Water compressibility 1/psi
To generate the file 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 a
message similar to
PROSPER table written to file: C:\Program
files\Infochem\Prosper1.pvt
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 or error message will be displayed
and the errors are reported in the output window.
CAPE-OPEN Interface
Infochem/KBC has been an active participant in developing and testing the
CAPE-OPEN (CO) standards. The Multiflash CO modules implement versions
1.0 and 1.1 of the standard and support the
PropertyPackageManager/ThermoSystem and PropertyPackage interfaces. The
interface has been tested for interoperability with Petro-SIM, Aspen+, CoCo,
ProII, gPROMS, Hysys and Simulis.
To generate a Multiflash CO Property Package for use with the Multiflash
CAPE-OPEN module simply set up the problem as usual. Instead of saving the
Problem Set-up choose the Export CO Property Package option from the File
menu. It is not necessary to specify which version of the CO interface you intend
to use.
For more information see the document the CAPE-OPEN Interface for
Multiflash 4.4 document which is installed when the interface is selected during
the installation of Multiflash.
PVTSim CHC file import tool
PVTSim is a general thermodynamic properties package of Calsep. The files
generated by PVTSim (.CHC files) can be easily imported into Multiflash to
perform thermodynamic calculations.
To import a CHC file simply:
1) Select Import PVTSim CHC file from the File menu. The following window
should appear:
2) Click the "Browse" button and search for the .CHC file that you desire to
import. Then click on the "Open" button.
3) Choose the options for model import regarding models for viscosity, thermal
conductivity, and surface tension. Otherwise the suggested default models will
be used.
4) Click on the phases you want to define. Otherwise the suggested default
phases will be defined.
5) Optional: if the original mixture as defined in the CHC file does not contain
water but water is desired in the mixture, simply click on the "Add water" tick
box.
6) Optional: use the GERG 2008 model to calculate the vapour phase density.
7) Click the "Import" button.
Help
Introduction
Help is provided in various ways:
 This document: User Guide for Multiflash for Windows
 On-line Help
 Website support
 Technical support
On-line help
The on-line help is accessed through the Help menu
Help Topics
Help Topics provides access to the Contents, Index and Search facilities for
Multiflash Help.
User Guide for Multiflash for Windows Help  191

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 the Search tab 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.
192  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.
Multiflash Error Codes

The error codes are the identification codes printed in the main window when an
error occurs. The code numbers may be entered and a short explanation is given.
Check for Updates

If your computer has an internet connection you can check for the latest update
for the version of Multiflash that you are running. For example

About Multiflash
The About option provides information about the Multiflash software and your
license. It is particularly useful when reporting any problems to Infochem’s
technical support team.
Version Info shows the version numbers of the Multiflash dll (the calculation
engine) and the GUI.
License Info includes your serial number and the expiry date of the license.
Contact details gives information on how to contact Infochem,
Location, Configuration and Log Files shows the path for the Multiflash
application location and log files which are set by the
Tools/Preferences/General/Folders option. You should check that these folders
are set correctly if you experience problems in accessing data or messages. For
further information see the Multiflash Installation Guide.
The configuration file is an optional Multiflash command file called
MFCONFIG.dat file that is run when Multiflash starts. If it is not found the file
is not listed.
The .log file is the file which automatically records the input and output
information for any run.
Technical support
To report bugs found in Multiflash, please email us. The support email address
is: software@kbcat.com.
If you need further assistance contact us at:
194  Help User Guide for Multiflash for Windows

Infochem/KBC Advanced Technologies plc.
Unit 4 The Flag Store
London SE1 2LP
UK
Telephone: +44 (0)20 7357 0800
Fax:+44 (0)20 7407 3927

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 containing the compound(s)
into Multiflash
 Load an existing problem setup file into Multiflash and edit the
problem to add the compound of interest
If you want to know the stored values for the temperature independent properties
or the correlation coefficients of a temperature dependent property choose Pure
Component Data from the Tools menu bar as described previously, see
“Viewing and editing pure component data” on page 70.
Defining the problem in Multiflash

Choose a suitable model for the problem. If you wish to obtain the properties as
set in the pure component databank choose 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 correlations 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:

From the Select menu choose Model Set and click on the Activity Models tab
and select Ideal Mixing for the liquid phase and Perfect Gas for the gas phase.
For transport properties choose the mixing rules models.
User Guide for Multiflash for Windows Case studies - Pure component data  197
Click on the Define Model button and then on OK,
For more information on models see “Models” on page 29.
Specify the pure component of interest
From the Select menu choose Components or click on the toolbar button
Specify the data source and component in the Select Components window
The default data source is the Infodata databank. To change this click on the
down-arrow to the right of the data source box and choose another databank
from the list.
Type the component name in the Enter name box and press the enter key or click
the Add button. Other ways of selecting components are described in the section
“Defining a mixture” on page 65 .
Specifying the physical property output level

If you are interested in pure component data you will probably want to output all
available calculated properties.
Choose the Property Output option from the Select menu.
Check the boxes for the properties you want given as output, e.g. heat capacity
and/or transport properties. Checking the volume and/or the heat capacity boxes
will also check all previous boxes, because those properties are required for
obtaining the requested property.
198  Case studies - Pure component data User Guide for Multiflash for Windows
Enter a 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 the Compositions button, and enter a value of 1.0
in the right-hand column of the table next to octane.
The input for this example is summarised in file octane.mfl.
Carry out a the flash calculation

To obtain the properties of liquid octane on the saturation line you must carry out
a bubble point calculation at a specified temperature.
Enter a temperature, say 400K in the temperature box in the Conditions section.
Click on the Bubble point at fixed temperature toolbar button to carry out
the calculation
The reported pressure is the saturated vapour pressure at 400K, the other
properties are listed below the phase equilibrium output. As we are dealing with
a pure component exactly the same property results would be obtained if we had
specified a dew point flash at the same temperature.
The next temperature can be entered in the temperature box in the Conditions
section and the bubble point flash repeated at this temperature.
Obtaining properties from the Pure Component

Data option
The output from a flash calculation does not directly contain any of the pure
component data values that are stored in a databank. To obtain this information
choose the Pure Component Data option from the Tools menu. The following
window is displayed
As we are dealing with a single component this will be the only choice available
and should be highlighted. Click on a property in the property list and double-
click or click on the Edit button to view or change the property. For constants the
properties are displayed in the current units but these can be changed. For
temperature-dependent properties such as the vapour pressure, the identifier of
the correlating equation and the equation coefficients are displayed. It is usually
not advisable to change correlation coefficients unless you are entering new
values from some alternative data source. The equation identifiers are defined in
the User Guide for Models and Physical Properties.
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 114.231 g/mol
TCRIT 569.32 K
PCRIT 2497000 Pa
VCRIT 2056.359 mol/m3
ACENTRICFACTOR 0.396
TBOIL 398.82 K
HFORMATION -208446.9 J/mol
SSTANDARD 466.7252 J/mol/K
TMELT 216.37 K
HMELT 20740. J/mol
SMELT J/mol/K
CPMELT 50.00791 J/mol/K
VMELT 50814.48 mol/m3
RUNIQUAC 5.8486
QUNIQUAC 4.9360
THLWATER K
VHLWATER m3/mol
DIPOLEMOMENT 0. debye
POLARIZABILITY Å3
QUADRUPOLEMOMENT debye Å
PARACHOR 351.4 (dyn cm-1) 1/4 cm3/mol
RADGYR 4.68040E-10 m
HOCASS 0.
GFORMATION 16000. J/mol
SFORMATION -752.7986 J/mol/K
TTRIPLE 216.38 K
PTRIPLE 2.1083 Pa
HCOMBUSTION -5074150 J/mol
V25 6120.925 mol/m3
SOLUPAR 15447.5 (J/m3)1/2
SOLIDSOLUPAR (J/m3)1/2
ZCRIT 0.2587676
REFRACTINDEX 1.39505
TFLASH 286. K
TAUTO 479. K
FLAMLOWER 0.8 vol %
FLAMUPPER 6.5 vol %
SPGRAVITY 0.7066211
EXPANSIVITY 1/K
OMARKS
OMBRKS
OMAPR
OMBPR
CNUMBER
REFVISCOSITY Pas
REFVISST Pas
REFVISPD Pas
REFVISTW Pas
REFVISLB Pas
LJEVISC J/K
LJBVISC m
EOSC
TYPE 1.
HDATUM 1.
SDATUM 1.
COMPREFNO 93.
MCRKS1
MCRKS2
MCRKS3
MCPR1
MCPR2
MCPR3
HYDOC
HYD1
HYD2
HYD3
ASSBETA
ASDBETA
ASSEPSILON J/mol
ASDEPSILON
ASSGAMMA
ASDGAMMA
ASSDELTA 1/K
ASDDELTA
ASSFF
ASDFF
ASSAC J m3/(mol)2
ASSBC m3/mol
ASSKAPPA
SAFTKAPPA
SAFTEPSILON K
SAFTGAMMA
SAFTFF
SAFTEK 242.78 K
SAFTSIGMA 3.8373E-10 m
SAFTLAMBDA
SAFTM 3.8176
SAFTQ
SAFTFRQ
VSRKS1 m3/mol
VSRKS2 m3/mol/K
VSRKS3 m3 K/mol
VSPR1 m3/mol
VSPR2 m3/mol/K
VSPR3 m3 K/mol
CPIDEAL 1. -32384.514 -3721.3925 4.
76 290. -1.3945 5.6339999
-5.7709999 0. 0. 10000.
CPSOLID 5. -24. 1.9471999 -0.0085359998
1.34E-5 2.094E-8 20. 216.37
PSAT 3. -7.9121099 1.38007 -3.8043499
-4.50132 260. 568.95
HVAP 1. 54909.031 .3775 0.
0. 0. 0. 568.381
LDENS 1. 2032.52 5407.5898 0.375
0. 568.381
LVISC 2. -20.462999 1497.4 1.3789999
0. 0. 216.38 398.83
VVISC 1. 3.1191E-08 0.92925 55.092
0. 216.38 1000.
LTHCOND 5. 0.21867631 -0.00038267 2.1762921e-7
0. 0. 216.38 500
VTHCOND 1. -8758. 0.8448 -2.71210E+10
0. 339. 1000.
STENSION 1. 0.05278999 1.2323 0.
0. 0. 216.38 568.7
CPLIQUID 5. 224.83 -0.18663 .00095890998
0. 0. 216.38 460.
SDENS 5. 8340.9004 -3.1515 0.
0. 0. 133.15 216.38
VIRIALCOEFF 1. .00027389999 -5.65219E-04 -3.63347E-04
-1.161662E-05 2.58796E-06 284.38 1500.
DIELECTRIC
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 User Guide for Models and Physical
Properties.
Excel interface
If you wish to produce tabular output or for graphical output for properties other
than phase boundaries the most convenient tool is the Multiflash Excel interface.
The example file PURE.xls shows how to construct the following table of
properties for octane.
Liquid properties on the saturation line
TEMP PRESSURE CP ENTHALPY DENSITY VISCOSITY THCOND SURTEN
Pa J/mol/K J/mol mol/m3 Pas W/m/K N/m

275 427.8 231.4 -47032 6255 0.0006945 0.1299 0.02341
300 2038. 247.7 -41043 6117 0.0004974 0.1235 0.02099

325 7232. 264.4 -34641 5970 0.0003783 0.1173 0.01861
350 20572. 281.4 -27819 5814 0.0003015 0.1114 0.01629
375 49414. 299.0 -20563 5646 0.0002493 0.1058 0.01404

400 104101. 317.4 -12856 5464 0.0002123 0.1004 0.01185
425 197831. 337.3 -4668 5265 0.0001839 0.09535 0.009729
450 346415. 359.7 4045 5042 0.0001605 0.09055 0.007696
475 568184. 386.4 13359 4788 0.0001412 0.08601 0.005760

500 884337 422.1 23420 4488 0.0001250 0.08175 0.003941
For more information on the Excel interface see the document: User Guide for
Multiflash Excel Interface.
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 “Getting Started” on page 13, 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, PR78 or RKS.
Select Select on the menu, then
Select Model set from the sub-menu, followed by
Selecting Equations of state Tab 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.
User Guide for Multiflash for Windows Case studies - Phase equilibria  205
Specify the components
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 66. As our current system contains
simple well known compounds they have been selected by
Choosing 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 it is:
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 either by doing a series of individual
bubble/dew point calculations, or by generating the phase envelope. Individual
calculations can either be at fixed temperature or pressure. Technically there is
206  Case studies - Phase equilibria User Guide for Multiflash for Windows
no particular reason to prefer one over the other; for this particular example we
will fix the temperature and have our output pressure in bar.
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 400K
you still have a stable solution reported, but by 425K you will notice a failure
message
Bubble point at fixed T:
*** WARNING -20323 ***
Possible instability in solution (constrained flash)
*** ERROR 20334 ***
Constrained flash solution unstable
*** ERROR 20028 ***
Cannot solve flash problem - other unspecified error
*** ERROR 344 ***
The flash calculation has not converged.
Investigating the bubble point curve using reduced temperature steps you will
see that the solution is stable up to 404K and fails at 406K. 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 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
fixed phase fraction route and looking for the upper retrograde solution.
To do this:
Click on the fixed phase 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 LIQUID1. Choose Mole Fraction under Select Basis and
enter a phase fraction of 0.0 in the text box and click on the Upper retrograde
type of solution. This fixed phase flash simulates a dew point calculation.
Click on Do flash.
The calculated dew point pressure is now 115 bar for the retrograde region,
whereas for the “normal” dew point the calculated pressure was 28.2 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 cricondentherm. You should now switch to fixed phase fraction flashes at
fixed temperature, set the options as described and reduce the temperature in
small steps. In this way the retrograde dew point curve can be generated back to
403 K.
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
70C 402.731 147.11
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 will 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 300K in the Conditions section of the main window.
Click on the fixed phase 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 “Defining petroleum fractions” on page 109.
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 the “Add/Remove Petroleum
Fractions” button to launch the Petroleum Fraction Input form.
Enter C7+ in the Component name column, 234 for Molecular Weight and
0.838 for specific gravity on the form.
Click on Calculate or OK button to include the fraction in the defined stream. If
Calculate button is clicked, the rest of the physical properties which will be
calculated are displayed in black on the form. The user-entered values are in red.
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 as follows
and click Calculate button
and Multiflash will determine the properties from a set of standard tables. The
calculated values by Multiflash are displayed in black and user-entered values
are in red.
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 -10539.6 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 273.134K.
You can also add the isenthalpic boundary for -10539.6 J/mol to your phase
envelope.
PVT Analysis
Many users will receive a PVT Analysis for 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 Lab Analysis” on page 89.
The case study we are considering here is based on a problem setup file called
pvt_anal2.mfl.
To enter a PVT Analysis when you have no measured n-paraffin distribution
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 data source for your discrete (i.e. well-defined) pure components.
This can be Infodata or DIPPR. In this example we use Infodata. Next at the top
of the column headed Single fluid you can 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. For this case the composition is
provided as mass%. 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 “Petroleum fluids” on
page 89. 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.
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. We’ve 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
The output lists the components and their composition in the units requested.
The additional column indicates the lower boundaries of the particular cut, for
example C6 comprises the cut from C5.5 to C6.5.
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.
You can include an n-paraffin distribution by ticking the Estimate Wax Content
box located in the PVT analysis form. Set the starting point for the n-paraffin to
N6 with 15 n-paraffins. In this case the names and compositions of the fraction
cuts will differ,
If you return to the PVT Lab Analysis form and instead of the heaviest SCN
choose "Single fluid" and enter a MW of 68. Do the characterisation (without n-
paraffins) 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. (The line for C8, 15PF is on top of the line for C20, 8PF).
Next, return to the original fluid definition and re-plot the phase envelope (first
clear the previous plot), then in the PVT Analysis form enter a water cut. 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 "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 by clicking on VLE AutoPlot.
User defined carbon number cuts

In the previous examples the carbon number cuts, SCN, have been defined by
the software. If you wish you can over-ride these by choosing your own SCN.
Starting with the pvt_anal2.mfl file go to the PVT Analysis form and change the
starting point for the pseudocomponents to C6 with five pseudocomponents. Do
the characterisation and return to the main window; you will see that the plus
fraction has been defined with five SCN cuts
Now, plot the phase envelope and then return to the PVT Analysis. This time
check the box for user defined cuts. Clicking on "Define Cuts" button will show
a drop down box that allows you to set the SCN cuts for the specified number of
pseudo components (in this case 5).
After setting the SCN to 6, 10, 20, 30, and 40, and performing the
characterization, the results window shows the amounts and starting points for
the new SCN.
For these user defined SCNs the phase envelope is identical to the original.
A more distorted distribution (e.g., with cuts at SCN of 6, 30, 35, 37, and 40),
may affect the phase envelope more.
TBP curves
If your PVT analysis data, instead of a detailed SCN/Composition report, is
based on assay data, such as a True Boiling Point (TBP) curve or a D86 analysis,
you can enter this and convert the data to fixed carbon number cuts.
Go to the PVT Analysis and click on the tab marked Distillation Curves and
enter your data. This case study is based on the TBP.mfl file, which has volume
% and boiling point data but no Molecular weight or specific gravity.
Once you have entered this, proceed as usual and do the characterisation If this is
successful the plot will show the comparison of data and fitted distribution,
and the carbon number distribution will be reported in the results window.
Once you have defined a fluid model you can carry out calculations or plot the
phase boundary as for any fluid.
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 compositional analysis. Our example is based on the blackoil.mfl file.
To do a black oil analysis open the PVT form and select the “Balck Oil
Analysis” tab.
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 chosen
split is 15 fractions from C6+. Clicking on Do Characterisation generates the
message that the characterisation has been successfully completed – 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.
Delumping tool – Case study
A simple fluid with only one petroleum fraction is used as a starting point for
this delumping example. The composition of the fluid is given in the following
table.
Example fluid:
Component Amount (mol)
Methane 95
Ethane 3
Propane 2
Co2 0.1
N2 0.15
C6+ 5
The C6+ fraction has the following properties:

Tc (K) Pc (Pa) Acentric factor Molecular weight
863 1.5e6 0.9 250
All the remaining properties will be calculated by Multiflash once this
information is entered in the Petroleum Fraction Input form from the Select
Components tool.
Save the file as “original_fluid.mfl”
After defining the fluid, click the delump button .
Click the “Delump” button.
From only one component in the plus fraction, 60 components were generated.
Now, click “Close” to close the delump tool. When prompted to use the
delumped fluid as it is click “yes”.
The resulting fluid may be saved into an MFL file for future reference with the
name “full_delumped.mfl”.
Open the Delumping tool again by clicking the “Delump” button. Click the
“Open PVT tool” button. The following window will appear:
Then, click “Do Characterisation” to characterise the fluid with the default
settings. Note that the first petroleum fraction is C14, which states that the
original C6+ was heavier than the name implied.
After characterising the fluid, with the default settings the resulting components
and amounts are displayed in Multiflash main window:
This fluid can now be saved in file named “delump_rechar.mfl”.
A comparison of the different fluids can now be made, in terms of the shape of
the phase envelope. As an example the default RKS (Advanced) model is used.
Note that this is a very simple example to illustrate how to use the delumping
tool. The delumping procedure is more reliable if the original fluid contains
more than 1 petroleum fraction. For this simple fluid the phase envelopes of the
delumped and the re-characterised fluids differ from the original fluid, while
better agreement is usually obtained when the original fluid contains more
information (more petroleum fractions).
An example with a more complex fluid and with wax is shown below.
Open the file “wax.mfl” that is shipped with Multiflash. In this file the original
fluid has 30 petroleum fractions.
Use the same procedure as described above. The resulting phase envelopes are
shown below:
Refrigerant mixtures
Several of our customers have used Multiflash to determine the properties of
refrigerants. A number of pure refrigerants are included in the INFODATA
databank and in the CSMA 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.mfl.
To determine the properties of any refrigerant mixture, first load refrig.mfl 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
R409B
R410A
R410B
R411A
R411B
R414B
R417A
R500
R501
R502
R503
R504
R507A
R508A
R508B
To determine the dew point properties of R407A

Load refrig.mfl
Load R407A.mfl
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
For polar systems, not related to oil and gas problems, the best model is often an
activity model, such as Wilson-E, NRTL, UNIQUAC or UNIFAC, but binary
interaction parameters are 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. The UNIFAC BIPs are generated
from group structures. 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. Described in ACETH2O.mfl. 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 61.4 degC and a vapour phase fraction of acetone of 0.821. 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 that the BIPs
must be in the correct 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 60.9 degC and a vapour phase fraction of acetone of 0.824.
Entering BIPs
You may have a mixture where there are no stored BIPs. Take for example the
system carbon tetrachloride/hexane. If you 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 Wilson-E model no BIPs are available.
Set the pressure to 1 bar, and specify the composition to 0.325

mole carbon tetrachloride and 0.675 mole hexane.
Click on the P, Bubble point flash button to see the model prediction using the
default, BIPs = 0.0.
The predicted result is a bubble point temperature at 1 bar of 344.3K and a
vapour phase fraction of carbon tetrachloride of .270. The experimental data is
342.8 K with y =0.286.
However, for this data set we have fitted BIPs for the WilsonE model; 266.61
and 461.91 J/mol. You can enter these BIPs 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 ensure that you WilsonBIP2 is the name recognised by Multiflash for BIPs relating to the
have specified the correct Wilson E model. This model has two BIPs, which may be expressed as constant,
units for the numeric values of linear or quadratic functions of temperature. The fitted BIPs like those from
the BIPs Dechema are temperature independent, i.e. constant. The BIPs are asymmetric
and not interchangeable. It is therefore important to input the values in the
correct order. If the BIPs are reported for pair A-B, the first value must go in the
cell in row A, column B, and the second value must go in the cell in row B,
column A.
If your BIP units are not the default J/mol change the units by clicking on the
Units button in the BIP box
Enter the new BIPs in the selected units
Click on OK and then on Close in the Show BIP values box.

Click again on the P, bubble point button.
This time the predicted bubble point temperature is 342.9K and the gas phase
composition is 0.288. 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 temperature again. with the BIPs.
You should reproduce the following results when the BIPs are entered in J/mol.
Temperature/K y1
Wilson E No BIPs 344.3 0.270
BIPs: 266.6, 461.9 342.9 0.288
UNIQUAC (VLE) No BIPs 344.2 0.271

BIPs: 208.5, -12.84 342.9 0.288
NRTL (VLE) No BIPs 344.0 0.273

BIPs: 276.8, 284.9, .3 342.7 0.287
UNIFAC (VLE) 343.4 0.279
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 system 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 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 will be
in K so you must choose the correct input units or convert them by multiplying
by the gas constant (8.314 JK-1mol-1).
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.
Two different warnings will be given depending on the problem:
*** WARNING -20001 ***
Unstable solution, more phases exist.
T =298.25K P=1.00000E+05Pa ? CONVERGED ..UNSTABLE

*** WARNING -20006 ***
Type of phases present do not agree with phase
descriptors.
These warnings 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 and water compositions to .5 mol each
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 that 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 preferable 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 identified at a mole fraction
of 0.46 propanol. The plot was generated using the Wilson-E model, and by
making a series of bubble point calculations at 1 bar at varying composition of
the liquid phase.
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
most easily seen using an Excel spreadsheet. An example would be a mixture of
benzene and naphthalene. 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 fixed phase fraction calculations to identify, for a given pressure, the
temperature at which solid benzene and solid naphthalene form. A plot of the
predicted temperature versus composition for both shows the eutectic point. For
the RKSA fluid phase model and 1 bar this is predicted to be at 269.9 K and a
mole fraction of benzene of .871.
Polymers
The PC-SAFT equation of state in Multiflash can be used to model 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
The Infochem/KBC databanks do not contain any data for polymer components.
Polymers should be defined 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. They are not required by the
PC-SAFT model, and therefore do not affect the calculated results. 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
molecular weight, 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.
Using PC-SAFT, every pseudocomponent for a given polymer must be assigned
the same values of the pure-compound parameters SAFTSIGMA (in metres, not
Ångstrom 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 1000000.019=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. As with CPA, in most cases it is the parameter, SAFTBIP that is
adjusted. As the polymer is non-volatile, changing the BIP may affect the phase
distribution and phase compositions more than the bubble point pressure or
temperature. The result of altering the SAFTBIP from 0.0 to .05 for our sample
system 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 and water in the
mixture. 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.
N.B. Occasionally the phase labels, LIQUID1 and LIQUID2 may be
interchanged. If this causes confusion they can be forced to stay the same by
defining a key component for one of the liquid phases. You can use the
Tools/Command menu option and enter the command
Key liquid2 heaviest:
Before PC-SAFT was implemented, 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 25°C (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.
Co-Polymers
PC-SAFT can also be applied to co-polymers. Multiflash allows the user to
define up to four polymer segments which can be used to define any number of
homopolymers or copolymers. If the polymer is formed from only one type of
segment, it is a homopolymer of that segment; if it is formed of two or more
types of segment, it is a copolymer.
We will look at an example where the constituent segments are ethylene and
propylene (PE and PP). The fluid is set up in the copol.mfl file. The appropriate
PC-SAFT parameters were taken from papers by Sadowski et al. as are the BIPs.
A co-polymer structure (PEP1) has to be defined, as well as the physical
properties of the co-polymer. The MW, T, P and acentric factor are required
although the latter three are only used as starting values and arbitrary numbers
may be assigned as long as Tc is high and Pc very low in line with the low
volatility of polymers. Next a “template” has to be created to indicate the
structure of the co-polymer. This is done by specifying "Bond Fractions", i.e.,
the total fraction of bonds between different type of segments. For example, in
the case where there are regular alternating ethylene and propylene segments, the
fraction of PP-PE bonds is equal to 1.0 (all bonds are of type PP-PE).
Conversely, the fractions of direct PE-PE or PP-PP bonds will be equal to zero
(no PE-PE or PP-PP bonds are present because the monomers alternate).
To specify the bond structure, we select Tools/Pure Component Data/SAFT
bond fractions. After clicking on Edit we get
The names of the constituent segments are entered as shown. The pattern of bond
fractions shown is that for an alternating co-polymer as described above. In the
case of a random co-polymer, the bond fraction pattern would be:
Bond Fracs
0.25
0.5 0.25
Our input file, copol.mfl, has a co-polymer with a MW of 96400 g/mol. It is
present at 15 wt% in a solvent, 1-butene (85 wt%). Calculation of the polymer
cloud point is a difficult calculation. You can calculate this using a series of P,T
flashes to see, for a given temperature, the pressure at which a second liquid
phase appears or disappears. Another useful technique is to set the temperature
of interest and calculate a bubble point. For this fluid the bubble point at 100
degC is shown below.
If you only have a gas and one liquid phase at the bubble point, then changing
the pressure will not result in a liquid-liquid separation. If at the bubble point
you have gas and two liquid phases then you can calculate the cloud point, the
point at which a second liquid phase appears, using the fixed phase fraction flash
at specified T, even though this is not completely straight forward. The solution
type should be set to “unspecified” and it may sometimes be necessary to use
starting values. Depending on the mixture you might need to look for liquid1
(rather than liquid2) to find the cloud point. That is the case for this fluid.
(Starting value for pressure should be 82 bar).
A PT flash calculation for this mixture at 100 degC and 83 bar returns one phase,
with label liquid1.
It might therefore be counterintuitive that to find the cloud point you need to
look for liquid1 rather than liquid2, but a flash at 100 degC and 82 bar shows us
that it really is the phase liquid1 which appears/disappears at the cloud point.
Labelling the phases for a system like this is not straight forward, which is the
reason for these somewhat surprising results. When two liquid phases are present
it is straight forward to keep track of which is which, in the sense that the solvent
phase is labelled liquid1 and the polymer phase is labelled liquid2. The problem
is when only one liquid phase is present. Because the amount of polymer is
reasonably small the combined phase is given the label of the solvent phase. This
is what causes the problem at the cloud point, where the solvent starts coming
out of the combined phase, and forms an almost pure solvent phase, and the new
phase really is liquid1, and the existing phase changes label to liquid2.
A complex picture of the phase behaviour of co-polymers of the same type but
differing molecular weight can be built up as shown in the following figure.
PEP of varying MW and 1-Butene

Wt% .15PEP:.85 Butene
300
M=.709kg/mol
250 M=5.9kg/mol
M=26kg/mol
200 M= 96.4kg/mol
P/bar
150
100
50
0
0 50 100 150 200 250
T/C
To specify the co-polymers of differing MW you need only change the MW

using Tools/Pure Component properties, all other SAFT properties remain the
same. Provided the overall composition is specified in mass units it will remain
the same even if the co-polymer MW is varied.
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 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,
even without considering the possibility of scale formation. 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 hydrates.
The models used in Multiflash for hydrates and hydrate inhibition have been
briefly described, see “Hydrate model” on page 39, 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 are used. The Hydrate model sets
contain a complete description of model and phase specifications.
To define a hydrate model, 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 conjunction
with one of the solid phases such as any hydrate phase or the ice phase.
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition  243
Therefore the selection of Phase Nucleation does not increase the number of
phases associated with the model used.
If you have a high concentration of salt then you may need to consider the
possibility of salt precipitation. Multiflash can consider the formation of chloride
and bromide scales. As this may not be a problem for many systems this option
is not considered by default. If you think you may have a problem you should
check the Halide Scales box. This will increase the number of phases that must
be considered but the additional phases will be added automatically when the
box is checked, the user does not have to do anything.
Fluid phase model

To carry out the full range of hydrate calculations with all the available
inhibitors the recommended fluid phase model is the CPA-Infochem. The CPA
model is based on advanced RKS equation of state with additional association
terms for describing the chemical association among the polar components such
as water and methanol.
Two sets of BIPs are required, one is required by the RKSA and another set is
required by the association terms to describe the cross association between polar
components. The required binary interaction parameters by CPA for
hydrocarbons, light gases, water and inhibitors are available from the BIP
databanks, INFOBIPS and the BIP correlations of OILANDGAS.
For inhibition with methanol, ethanol, MEG, DEG or TEG, CPA is the
recommended model as it reproduces the partitioning of methanol and MEG
between water and hydrocarbon vapour and liquid phases more accurately than
RKSA-Infochem with the Modified NRTL Infochem mixing rule.
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.
244  Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
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/KBC 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/KBC 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.
Scale model
In its general form, the freeze-out model can be applied to any solid phase of
fixed composition, which must be defined. The model can for example be
applied to hydrated salts such as monoethylene glycol (MEG) monohydrate or to
crystalline mineral salts, i.e. scales.
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.
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 1 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 both hydrates and 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 nucleation temperature is higher than the dissociation
temperature. However, this is not a real situation as ice is not being considered
except for nucleation.
If Halide scales are to be considered then further phase descriptors are required.
These must represent the correct fixed composition of the scale, these are: NaCl,
NaCl.2H2O, KCl, CaCl2.2H2O, CaCl2.4H2O, CaCl2.6H2O, NaBr,
NaBr.2(H2O), KBr, CaBr2.6(H2O).
The addition of these phase descriptors is done automatically by Multiflash when
the "halide scales" option is selected.
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.
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 hydrate.mfl, which describes a gas condensate.
From the Select menu choose Model Set and click on the Hydrates tab. In the
dialog box, select the relevant phases required and initially specify CPA as the
fluid phase model.
Click on OK once the hydrate model set has been successfully defined and
loaded.
Specifying the components and composition
The fluid for this case study is defined in the following table:
Component Moles
METHANE 85.93
ETHANE 6.75
PROPANE 3.13
ISOBUTANE 0.71
BUTANE 0.88
PENTANE 0.57
CO2 1.31
N2 0.72
WATER 10
Define the normal 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.
Close to go back to the main window. Click on composition and enter the
correct number of moles for each component.
Alternatively. Load the hydrate.mfl input file.
Enter the temperature, 270K and the pressure, 1 MPa (remember to change the
standard pressure units from Pa to MPa). The input units are defined in moles
but the output units for this example are in g.
Click on the P,T flash button
You will see the following results in the results window.
Hydrate2 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. Clicking on the Phase Envelope
button , selecting Hydrate 2 phase and setting HYDRATE2 phase fraction
equal to 0.0, the HYDRATE2 phase boundary can be generated by clicking the
Plot button.
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 hydrates occurs and
hydrates will form. Between these two points is the area of hydrate risk where
hydrates may or may not form depending on the time scale (see figure below)
and the kinetic consideration.
P
H yd r a t e z o n e H yd r a t e H yd r a t e fr ee
r r is k
e
s
s
u
r H yd r a t e fo r m a t io n cu r ve H yd r a t e d is s o cia t io n cu r ve
e
Tem pera ture
To calculate the hydrate dissociation temperature at given pressure

Retain the pressure at 1 MPa.
Either Click on the Hydrate dissociation T at fixed P button, or the Fixed

Phase Fraction Flash at specified pressure button,
In the first case Multiflash will determine the most stable hydrate structure and
report the dissociation temperature for this. In the second case a dialogue box
will be 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 2 is the most stable form and first begins to form at
276.1K.
It is important with the fixed phase fraction flash 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 were to be more
stable it would 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 hydrate
structures are stable at any T and P.
Hydrate formation temperature at given pressure

To calculate the hydrate formation temperature at 1 MPa, make sure the
nucleation model has been defined: go to Select/Model Set/Hydrates, check
the "Phase Nucleation" box and click on "Define Model". The nucleation
calculation will not work unless the model has been correctly defined.
Then, go to the Fixed Phase Fraction Flash – at specified P dialog box and
select Nucleation from “Select basis” . Set the phase fraction text box to zero as
before and then click the "Do flash" button.
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 appear:
If this happens, define the nucleation model by selecting "Phase Nucleation" in

the Hydrates model dialog box and repeat the calculation.
The calculated results with the nucleation model are displayed in the main
screen. Note that the hydrate formation temperature at 1 MPa is now 268K,
about 8 Kelvin lower than the hydrate dissociation temperature, 276.1K.
Note that the nucleation calculation is, in the thermodynamic sense, inherently
unstable, as reported.
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 270K.
The hydrate first forms at 0.598 MPa. 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 1.26 MPa.
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 - and add experimental
data if available.
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 212.
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. Multiflash
can achieve this by means of a "tolerance calculation".
The tolerance calculation combines two mixtures in different ratios
until a specified condition is met. The following example finds the maximum
water content for the above mixture at 270K and 1 MPa before hydrates will
form.
In order to calculate this, the following steps are required:
Click on Composition and enter 0.0 for the amount of water. The overall
compositions must be specified on a water-free basis, but water must remain in
the components list.
Then, select Calculate from the menu bar, and select Tolerance Calculation.
Then, select the required phase from "Select phase" box by clicking the
downward-arrow on the right side of the box. In this example, the phase should
be HYDRATE2. Set the 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 (i.e., pure water) 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 amount of second fluid added is the number of grams 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 at the chosen P and T.
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 79 ) 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 fluid 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 the gas defined previously in contact with a solution of water plus
methanol at a methanol fraction of 20% by mass. Using Tools/Inhibitor
Calculator bring up the Inhibitor calculator window and add 20 mass%
methanol to the 10 mole of water in the system.
After pressing the Add button, the following window will show up stating that
20 wt% methanol is approximately equivalent to adding 1.405 moles of
methanol to 10 mole of water
With the temperature at 270K and a pressure of 1 MPa

Click on the P,T flash button.
The results show that the addition of this concentration of methanol is sufficient
to prevent hydrate formation even though some has been lost to the gas phase.
Hydrate dissociation temperature at a given

pressure
With the same mixture, calculate the hydrate dissociation temperature using the
Hydrate dissociation T at given P button or the fixed phase 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
276.1 K to 266.5 K. 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 use the Hydrate
dissociation at given T button, , or specify a fixed phase fraction flash at
fixed T. The hydrate dissociation pressure increases from 0.598 MPa to 1.51
MPa. 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 270K
and 1 MPa.
Remove methanol from the main stream by clicking on Composition and
entering 0.0 mol for methanol. Note that methanol must still be in the
Composition list.
Select Calculate, then Tolerance Calculation to activate the Tolerance
Calculation dialogue box.
Select the required phase (HYDRATE2) from Select phase box.
Set this 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 1.3% on a mass basis with
respect to the total stream, approximately 13.6 mass % with respect to water in
the feed. The amount of second fluid added is the number of grams of the
mixture specified by the tolerance calculation (in this case pure methanol) which
must be mixed with the original inhibitor-free stream to meet the condition of
zero hydrate phases
Salt inhibition
The Electrolyte model treats the salts either as being composed of only Na+ and
Cl- ions or of Na+, K+, Ca++ , Cl- and Br- 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 81 that converts various analyses into
the equivalent amount of sodium, potassium, calcium, chloride and bromide
ions.
Load the hydrate.mfl file:
Change the Model set from CPA-Infochem to CPA-Infochem + Electrolyte
(Remember to Define Model).
Select the Inhibitor Calculator from the Tools menu and the tab “Salts / Ions /
Salt Analysis”
For this particular example there is information on the composition of the
formation water.
mass%
NaCl 6.993
CaCl2 0.735
MgCl2 0.186
KCl 0.066
SrCl2 0.099
BaCl2 0.036
Enter this data into the Salt Calculator
By clicking on Add the Salinity Calculator will determine the ion concentration
that needs to be added to the 10 mole of water in the mixture.
and this amount will be automatically 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 1 MPa for this
stream is reduced from 276.1K to 272.77K.
Scale precipitation
This feature allows for precipitation of NaCl, NaCl.2(H2O), KCl,
CaCl2.6(H2O), CaCl.4(H2O), CaCl.2)H2O), NaBr, NaBr.2(H2O), KBr and
CaBr2.6(H2O). This is activated by ticking the Halide Scales box in the
Hydrates Model Set but can only be defined with “CPA Infochem + Electrolyte”
fluid phase model option. If you have not specified such an option a warning
message is generated.
For our example the salt concentration is not high enough to trigger the
precipitation of a scale for hydrate calculations at 1 MPa. In principle, you can
use fixed phase fraction flashes to see when any of the scales will form. But the
temperatures may well be below those of operational interest. For example
selecting NaCl.2(H2O)
We and performing the fixed phase flash, we obtain
A similar calculation looking for the formation of CaCl2.6(H2O) produces seven
phases but at 240.6K.
A more likely scenario occurs if the salt concentration is higher, e.g. 30wt%
equivalent of NaCl. A flash at temperatures higher than hydrate dissociation
conditions will show NaCl forming
whereas at the lower temperatures where a hydrate phase is present you will see
NaCl.2(H2O) being formed.
Case studies – Wax precipitation
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
iso-paraffins 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 precipitation it is worth referring to a
paper by Erickson et al. SPE 26604, (1993). 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 ºF, the maximum difference was 55 ºF, whilst the average
difference was 24 ºF. 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. We recommend measurements made by Cross Polar
Microscopy (CPM) if available.
We also recommend that positive amounts of precipitated wax are used to
identify the WAT, rather than the strict thermodynamic interpretation of zero
percent, the onset of wax phase formation. The suggested default values are
0.045 wt% for reproducing CPM measurements and 0.3 wt% for DSC. The
equivalent defaults for mol% are 0.015 mol% for CPM and 0.1 mol% for DSC
but there is no automatic conversion between mass and mol%. The mass or
mole% of wax is related to the liquid plus wax phases.
Defining the wax model

The wax model in Multiflash is based on work by Coutinho. For more details
refer to the “Modelling wax precipitation” section on page 42.
The Coutinho wax model is a solid solution model which requires information
on the normal paraffins in the fluid. Predictions from the model are largely
governed by the n-paraffin distribution. If no experimental data are available for
the distribution it can be estimated from the total wax content. If these data too
are lacking then Multiflash has procedures to estimate an n-paraffin distribution.
Note that the estimation method is only valid for oils, not waxy condensates.
The n-paraffin distribution may be defined differently from that for the
remaining fluid 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.
260  Case studies – Wax precipitation User Guide for Multiflash for Windows
With a limited experimental data set it is not possible to make any definitive
statements concerning the accuracy of the model in predicting the WAT.
However it is clear that Coutinho's model provides a much improved prediction
of the amount of wax precipitated as a function of temperature compared with
other published thermodynamic models.
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.
Click the 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 Lab Analysis” on page 89. If you have an n-paraffin
distribution then you should open the PVT Analysis with n-paraffins using the
button. However, in this example (input file wax.mfl), there is no n-paraffin
distribution, only a wax content. So, in this case you should use the normal
button.
Enter the fluid composition and set both the pseudocomponents and n-paraffins
to be split from C6 (or N6) into fifteen fractions.
User Guide for Multiflash for Windows Case studies – Wax precipitation  261
If you fail to enter a wax content or to ask for this to be estimated then you will
still be able to characterise the fluid, but when you try to calculate the WAT you
will see a warning message box indicating that you don’t have an n-paraffin
distribution.
Provided you have n-paraffins in your fluid characterisation, you can then
calculate the WAT at any pressure, by using the WAT, button.
The pressure will be taken from the Pressure text box in the main window. From
a study of many waxy fluids we recommend using a small positive amount of
wax to identify the WAT and suggest default values for the most common
measurement techniques. The default for CPM is preset, but this can be altered
to any value, including 0%. Click on Calculate WAT to initiate the calculation.
Our example for this case study is based on a supplied problem set up file called
wax.mfl. This particular fluid has a reported experimental WAT based on two
different measurement techniques. At 1 bar, using CPM the reported WAT was
53ºC and using DSC was 40 ºC. The predicted WAT for the CPM default is
49.5ºC and for the suggested DSC default is 37.7ºC.
You may wish to vary the n-paraffin distribution for the Coutinho model and see
the effect on the predicted WAT. One suggestion is to extend the heavy end as
far as possible. You can do this by setting the start of the n-paraffin distribution
to something like N90 and only splitting into 1 n-paraffin. You will be warned
that the distribution has been extended as far as possible and the highest n-
paraffin will be lower than the N90 set. In this case the heaviest n-paraffin is n-
76+ and the WAT for the CPM default is 46.4 C. Extending the n-paraffin
distribution does not necessarily increase the WAT, as there are competing
effects from both the properties of the new heaviest n-paraffin and the solubility
of the reduced amount of this fraction.
If you have measured values for the WAT, then you can tune the
pseudocomponent properties for the model to match these values. This is done
using the Tools/Matching/Wax Phase option. The Matching option is described
in “Matching wax data/WAT” on page 123.
For this particular example we can take the WAT at 1 bar to be 53ºC from the
CPM measurement and use the characterisation as before where the n-paraffin
lumping starts after N90, leading to a single continuous SCN n-paraffin
distribution. Then enter the value or values for the WAT temperatures and
corresponding pressures and phase fractions. The fraction chosen can be zero but
should probably reflect the suggested defaults for the technique used for the
WAT measurement.
The matching facility will amend the values for the melting temperature and the
change of enthalpy on melting of the n-paraffin fractions.
The wax boundary can be plotted using the phase envelope button and choosing
the WAX phase. For plotting a wax phase boundary with a finite amount of wax
present to reflect the technique used in the wax measurements, the value such as
0.045wt% by CPM and 0.3 wt% by DSC has to be converted to the value related
to the total fluid if the gas phase is present. In this case, where we are
considering dead oil, 0.00045 mass fraction may be used to plot the wax phase
boundary.
For a live oil the amount of wax will be defined with respect to the total fluid.
This will vary with pressure, so in this case it may be better to choose a zero
mass fraction for the plot. The wax boundary for a live oil has a distinctly
different shape. The D marks the point where the wax boundary crosses the
bubble point line.
The full range of flashes is available for the Wax model.
Calculating wax precipitation

As with other phases, the amount and composition of the wax phase are
determined as part of any flash calculations. Given the uncertainty of the WAT
from some experimental techniques and the sensitivity of WAT calculations to
the characterisation of the heaviest fractions, a better picture of wax precipitation
can be derived from a calculation of the wax precipitated as a function of
temperature at a given pressure.
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, a simpler way of performing this analysis is to
use the wax precipitation curve button, . Clicking on this will activate the
wax precipitation curve form to produce a table of wax mass percentage as a
function of temperature with respect to the liquid plus wax precipitated at a
given pressure. The default starting temperature is 0°C, or the equivalent in other
units, and the finishing temperature is the calculated WAT for zero percent wax.
There is also an option to set the starting temperature to any other value. The
maximum number of points is twenty but the actual number of points will
depend on the WAT, the units used and a sensible step.
The pressure will be taken as that specified in the pressure text box on the wax
precipitation curve form. The wax precipitation curve below was generated using
wax.mfl as supplied. The numeric values are also reported in the main window
of Multiflash. A series of wax precipitation curves can be calculated within the
form to see the effect of pressures on the amount of waxes precipitated.
If you require additional results below 0 ºC, you can also use a command entered
in the Tools/Command box. The format of the command is:
WAXPC value_pressure value_Tstart value_Tincrement;
The wax precipitation curve calculated from the specified starting value is
reported in the main window.
Additionally, you can use the Add Data button to add the measured WAT if you
wish. The calculated values and the experimental data can be exported to an
Excel file from the form for further editing if necessary.
Case studies – Asphaltene
flocculation
Introduction
One of the major problems for the oil industry is the precipitation of heavy
organics during production, transportation and 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
additional terms to describe the association of asphaltene molecules and their
solvation by resins. The parameters for the model were initially developed from
a study of nearly thirty sets of experimental measurements of asphaltene
precipitation 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 precipitation from live oils. We are aware that many users have only
titration data for dead (STO) oils. We have investigated how to use 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 of a stock
tank oil.
 One set of asphaltene precipitation conditions.
User Guide for Multiflash for Windows Case studies – Asphaltene flocculation  267
 Bubble point (optional) to “tune” the petroleum fraction properties.
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 in the stock tank oil 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.
The % asphaltene is taken to be that precipitated by n-heptane. Some
laboratories report the wt % asphaltene precipitated by n-pentane. It is difficult
to give exact guidance on how to convert the values of asphaltenes between n-
pentane and n-heptane precipitation as this can vary from oil to oil and
laboratory to laboratory. In general we have found that the wt % asphaltene
precipitated by n-pentane is approximately twice that precipitated by n-heptane.
However, ratios may vary from 1.3 to 2.7.
If you do not have the complete data set 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 precipitation is not as sensitive to the
characterisation of the fluid as the wax model. The PVT characterisation method
has been improved to characterise asphaltenes correctly regardless of the number
of pseudo-components requested for the whole fluid. However, we suggest you
consider using a common characterisation procedure for any comparison. By
default, the PVT Analysis facility starts the pseudocomponent split at C6 and
split the fractions into 15 components.
Finally, to model asphaltene precipitation reliably, two model parameters should
be determined by matching two asphaltene precipitation onset data at two
different temperatures. If such experimental data are available, then the data
should be used to optimize the model parameters to reproduce the experimental
data. If you do not have asphaltene precipitation onset data, two additional data
may be used for tuning. They are the STO asphaltene titration onset data using
n-heptane and reservoir condition. Using reservoir condition, based on the
screening procedure suggested by de Boer et al (SPE 24987, 1992), assumes that
the asphaltene is nearly saturated at the reservoir condition.
Defining the asphaltene model

The cubic equation of state, RKSA, is defined as part of the model and it is not
possible to choose a different fluid phase model.
To set up the asphaltene model use the Select/Model Set menu option.
Select the Asphaltenes tab, Click on Define Model to select the asphaltene
model and Click on Close to return to the main window.
268  Case studies – Asphaltene flocculation User Guide for Multiflash for Windows
The default phases for the asphaltene model are gas, liquid1 and asphaltene. In
principle the Water phase can be included but the asphaltene model is developed
with the reservoir fluids that water is not considered. Therefore it is better not to
include water phase.
However if water is included in the fluid, the asphaltene model parameters
should be produced for the fluid composition excluding water. In this case, more
caution should be taken when plotting the asphaltene phase envelopes as the
presence of water in the mixture makes the phase equilibrium calculation more
complex.
The next step is to characterise your fluid. Go to the PVT Analysis form,
described in detail in “PVT Lab Analysis” on page 89. 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 next 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 don’t have so 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 show a plot of the data and fitted distribution. 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 Lab Analysis” on page 89.
The asphaltene model in Multiflash was developed based on experimental data
where the resin/asphaltene (R/A) 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 technique.
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. Initially, on
characterisation you will be warned of a possible problem.
You can ignore this warning message and see if model parameters can still be
produced. You can also increase the resin/asphaltene ratio manually or delete the
Resin amount from the SARA Analysis and tick the Estimate RA box in which
case the model will generate a default R/A ratio.
After characterisation the asphaltene component is named as ASPHALTENE,
and the resin component(s) by an “R” prefix, e.g. R65+.
Asphaltene matching
The next stage is to use the matching facility to “tune” the pseudocomponent
properties and optimize the asphaltene model parameter.
Multiflash allows for different tuning methods, based on the available
experimental data. The matching of the bubble points is recommended,
especially for light oils, although not always necessary. In any case, the use of
the matching procedure for the asphaltene phase is strongly recommended.
Although the default asphaltene model parameters are available for the case
where no information is available, it is usually not recommended to use the
default setting. For any cases without any measured asphaltene data, it is
recommended at lease that the reservoir condition should be used to tune the
model parameters.
For matching multiple bubble points, we suggest you to use the Tools/Matching
Bubble point form first before matching any asphaltene data. On the other hand,
if you have only one measured bubble point, the bubbelpoint can be specified on
the asphaltene matching form together with the asphaltene data. Note that the
bubble point is always matched first before matching the asphaltene data.
For this example we have several bubble points. Enter these into the
Tool/Matching/Bubble point table.
Click on Match to generate the comparison of predicted and matched data.
Use the Tools/Matching/Asphaltene Phase to display the dialogue box, and enter
the available data to obtain the asphaltene model parameters.
There are three types of asphaltene data that can be used for tuning the
asphaltene model parameters, which are summarised as follows.
1. Asphaltene upper onset data, ideally at two different temperatures.
2. Asphaltene onset titration data
3. Reservoir conditions (pressure and temperature)
In our example below, we have used the reservoir conditions (241 oF, 8500 psi).
Click on Match and then on Close: the optimised model parameter values will
be displayed in the main window. The asphaltene model has now been defined.
PLEASE NOTE: If all the three asphaltene data sets mentioned above are
available, the most adequate data would be the asphaltene upper onsets, followed
by the titration data and finally the reservoir conditions. Only one set of data will
be saved in the MFL file after matching.
Saturation P at reservoir T
In the case where only one asphaltene upper onset is available, the reservoir
saturation pressure could be treated as an another asphaltene upper onset
pressure at reservoir temperature provided that no asphaltene precipitation is
found experimentally at the reservoir condition. The reservoir saturation
pressure at reservoir temperature is usually measured. If not, the calculated
saturation pressure at the reservoir temperature can be used instead.
Calculating asphaltene precipitation conditions

Once the asphaltene model has been defined and the parameters generated you
can carry out asphaltene precipitation calculations.
If you are starting from the position where you only know the reservoir
conditions and have no information on specific precipitation 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 to follow the procedure
below.
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
1000 psi.
Click on Plot to display the phase boundary. This will usually show a point, or
points, of discontinuity at high pressure, labelled D. This is the point where the
asphaltene precipitation envelope crosses the bubble point line.
These points can be very useful for setting an appropriate starting pressure for
the asphaltene phase envelope or for 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 of the asphaltene phase to zero,
 the solution type to unspecified
 the Initial value for pressure to 3500 psi with pressure
increasing.
After clicking on Plot button, Multiflash will ask if you want more points to be
plotted. Click Yes, until the asphaltene boundary becomes complete.
For other examples you may have to set the pressure to decrease or to plot the
upper and lower boundaries separately. The upper boundary uses the
Unspecified solution or Upper retrograde type solution, while the lower
boundary, select the Normal 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 200 F and 4000 psi, Click on the P,T icon, or Select the
P,T flash from the Calculate\Standard flashes menu. The phases present, and the
composition and amount of each phase, will be reported in the main window.
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 precipitate at
any given temperature then you should use a flash at fixed phase fraction and
temperature. Set the temperature, in this case 200 F. Click on the icon or select
the calculation option and the dialogue box will be displayed.
Select the ASPHALTENE phase and 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 7958.74 psi. 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 Normal. In this case the reported
pressure is 1865.08 psi.
You can determine the amount of asphaltene precipitated at any set of P,T
conditions using an PT flash as described earlier.
However, a simpler way for understanding the asphaltene precipitation as a
function of pressure is to use the asphaltene precipitation curve button, .
Clicking on this will activate the asphaltene precipitation curve form to produce
a table of the asphaltene mass percentage as a function of pressures with respect
to the liquid plus asphaltene precipitated at a given temperature. The starting
pressure depends on the asphaltene precipitation upper onset pressure and the
finishing pressure is related to the lower boundary of the asphaltene precipitation
onset. The temperature will be taken as that specified in the temperature text box
on the asphaltene precipitation curve form.
The asphaltene precipitation curve below was generated using asphex.mfl. Load
this file, re-characterise the fluid, match the bubble points and then match the
asphaltene phase using the reservoir conditions, as explained before. A series of
asphaltene precipitation curves can then be calculated within the form to see the
effect of temperature on the amount of asphaltenes precipitated. The maximum
point in the precipitation curve corresponds to the bubblepoint, where the
asphaltene precipitation reaches its maximum.
If the temperature specified is outside of the asphaltene phase boundary, a

warning message will be generated as follows, indicating that there is no
asphaltene precipitation at the specified temperature.
Sensitivity of calculations to variation in input data
Choice of Analysis method

The previous calculations were carried out by characterising the fluid without an
explicit n-paraffin distribution and matching to reservoir conditions. The plots
below show the effect of including the n-paraffin distribution. Note that any re-
characterisation will reset all the matched model parameters to the default.
Therefore the experimental data must be matched again after re-characterisation,
in this case the bubble points and the asphaltene parameters.
The explicit inclusion of the n-paraffins for this case shows a small difference to
the predicted asphaltene phase envelope (APE) in the low temperature region.
This is mainly related to the change of the fluid due to the presence of n-
paraffins and the reservoir conditions data that are used to adjust the model
parameters.
However, if two asphaltene upper onset data are available for adjusting the
model parameters, the difference in the asphaltene envelope caused by the
presence of n-paraffins will be reduced. The formation of a solid wax phase
actually enhances the asphaltene solubility in the oil for this case and the
asphaltene envelope in the low temperature region is lowered as a result of the
presence of solid waxes. The new marked “D” along the asphaltene envelope are
the points where the wax phase boundary cross the asphaltene phase envelope.
For more details on simultaneously calculating asphaltene, wax and hydrate solid
phases, refer to “Case studies – Combined solids” on page 287.
Data Availability
This example of asphaltene precipitation was based on a data set which
comprised the compositional fluid analysis, a SARA analysis, bubble points and
the reservoir conditions. In this case, the bubble points were close to the
unmatched predictions and so matching to bubble points might not be expected
to make a major difference to the asphaltene predictions. However, even in this
case you can see a noticeable effect from the matching.
There are other data that may be missing and have an effect on the predictions.
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 are 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 precipitation envelope (APE). It is important to
include this step; the matched properties are re-set to default values 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 predicted weight % of
asphaltene is very close to the reported value with 0.7 wt% asphaltene predicted
compared to the experimental data of 0.5 wt%.
No resin – asphaltene ratio
Even if you do not have a SARA analysis you may have the weight %
asphaltene. In that case you only need to estimate the Resin/Asphaltene ratio.
Proceed as before, enter the wt% asphaltene (0.5 %) 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 APE.
Although the estimated R/A ratio is lower, at 13, than the original, at 22, the
resultant APE is very close. This is the result of two factors: once you reach a
certain level of R/A the effect of increasing the R/A is reduced and the difference
is compensated by slightly different model parameters obtained from matching
to a specific precipitation point or reservoir condition.
No reservoir pressure
If you only have the reservoir temperature we have included a facility to estimate
this. Simply enter the bubble point data and reservoir temperature as before and
initiate the matching procedure.
For this particular example the resultant APE is reasonably close to the APE
calculated from the real reservoir conditions.
As a corollary to this we have noticed that you usually generate very
conservative APEs 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 the bubble point is matched at a different temperature from the reservoir
temperature no warning is issued.
No reservoir or precipitation conditions

If you do not have either reservoir or precipitation 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 precipitation 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
precipitation, the model parameters are generated from correlations based on
data held in our database. On the Asphaltene matching form, just click the Match
button to generate the default model parameters. This will generate a warning
message. Then click OK to close the form.
The results from using this route are very variable, depending on the fluid
analysis and we cannot fully recommend its use. In this case the result would be
a much more conservative APE.
Matching to asphaltene deposition data

The assumption in this case is that you have more data than our basic example,
real asphaltene precipitation data either from field conditions or an asphaltene
precipitation measurement. In this case we have two asphaltene precipitation
onset points at 241 F and 6921 psi and 120 F and 9150 psi. Simply enter these in
the Asphaltene matching box instead of the Reservoir conditions.
For comparison purposes we have matched to each point individually and then to
both points.
To add data to the plot, you can use the Add Data option in the phase envelope
plotter to include the measured precipitation points and the reservoir conditions.
Gas injection
It is known that as gas is injected into a reservoir the likelihood of asphaltene
precipitation is increased. The asphaltene model predicts this trend correctly.
Return to the original APE, calculated from the asphex.mfl input file with
matched bubble points 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 8.32g to 12g
and re-plot the APE you will see that the fluid bubble point line is at higher
pressures and the APE has expanded.
When looking at the effect of gas injection you should, of course, not rematch
the fluid bubble point or asphaltene precipitation data as doing this will alter the
petroleum fraction properties and set the matched model parameters to the
default values. Usually the model parameters are matched with the asphaltene
precipitation data of the original reservoir fluid, and then the same model
parameters are used for modelling the asphaltene phase behaviour of the original
reservoir fluids with gas injection.
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 or use the
blending procedure in Multiflash to blend the injection gas stream and the
reservoir fluid.
Please note that the reservoir fluid with bubblepoints matched and asphaltene
model tuned should be selected for the model definition in the blending form, so
that the asphaltene model parameters are based on the original reservoir fluid. If
the asphaltene precipitation data are available for the blended mixtures, the data
should be matched after blending.
Titration
The Infochem/KBC asphaltene model is intended for use in predicting the
asphaltene phase behaviour of live oils and the generation of the model
parameters is based on asphaltene studies of live fluids. However, live oil
asphaltene studies can be expensive, particularly with the requirement to obtain
and transport bottom hole samples. Some of our users have asked whether
titration measurements on dead oils could 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
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
the procedure for using titration data has been automated.
The studies have been limited to titration with n-heptane.
Our example is based on the titration.mfl file provided. The file includes the live
oil composition and the wt% of asphaltene and resins. The reported value of
asphaltene was 1.9 wt%, that of resins was 16.1 wt% for the STO. Characterise
the fluid composition as usual and return to the main menu. Then go to
Tools/Matching/Asphaltene phase. The reported onset amount of heptane to just
cause asphaltenes to precipitate from the STO at ambient conditions is 1.4 cm3
per g tank oil. This has been converted to .962 g n-heptane using the known
density. Enter this value and the bubble point (54.4 ºC and 156.2 bar) and click
on Match.
The asphaltene model parameters will be reported in the main window as usual
and the APE can now be plotted. The resultant APE is compared below to those
generated from matching to a known flocculation point of 54.4 ºC and 200 bar
and to a combination of reservoir temperature (54.4º C) and bubble point (54.4
ºC and 156.2 bar)
The APE predicted from matching to titration of the STO is very close to the
APE from asphaltene precipitation measurements and both are 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 required to initiate
asphaltene precipitation and if this has to be deduced from other titration results,
then the procedure for parameter generation is slightly more complicated and
requires the use of an Excel spreadsheet. In the Multiflash GUI either
characterise the STO, if this composition is provided, or flash the characterised
live oil to STO conditions, using the RKSA model to ensure that no separate
asphaltene phase is formed. If you have bubble point data it is important that you
match these before flashing to STO conditions. Using the STO composition,
change the model set to asphaltene, match the asphaltene precipitation to
ambient conditions and save the problem using the File/Save Problem Setup
option.
You then need to create an Excel worksheet to read this .mfl file. Details of how
to do this are described in the Excel manual, but we have provided an example
spreadsheet, titration_sto.xls.
For our example we have generated the file STO.mfl from the fluid used in our
titration example. This is the file that should be used in the Excel spreadsheet. In
the spreadsheet you then need to do two things: add a new component to the list,
heptane, and add a command line describing the asphaltene parameters. This can
be copied from the Multiflash GUI by using Tools/Show/Problem to display the
commands. The command line can be copied and pasted to the spreadsheet but
for fitting purposes 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\sto.mfl";
model MREFASPHALTENE RAEQUIL DATA AAPREEXP
1.00000000 AAEXP 1.00000000 RAPREEXP
.636986
RAEXP
0.96698
;
component heptane;
The spreadsheet, titration_sto.xls, is set up to optimise the value of RAPREEXP
(RAP) using the Excel Tools/Solver by comparing the calculated wt% of
asphaltene deposited for given amounts of heptane to the experimental wt%
deposited.
For our particular example the data reported in the paper included a live oil and a
STO composition, a wt% asphaltene for the STO, an asphaltene precipitation
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 precipitation point using the matching facility produced the
following parameters
RAP 0.94176
RAE 0.96636
Whereas fitting to the other four points in Excel gave parameters
RAP 0.94999
RAE 0.96636
These parameters represent the STO titration data well, but the amount of
heptane to just initiate precipitation is slightly higher. You can check the
predicted value for the amount of n-heptane required for the onset of asphaltene
precipitation using a tolerance calculation with heptane as the second fluid. The
predicted amount is .997 g/g oil rather than .962.
wt% asphaltene component precipitated as Fn C7 solvent
2.00
1.80
1.60
1.40
wt% asphaltene
1.20
1.00
RAP fit
0.80 Exptl
0.60 predicted onset
0.40
0.20
0.00
0.000 5.000 10.000 15.000 20.000 25.000 30.000 35.000 40.000
g C7/g oil
It is clearly preferable to generate the live oil APE from live oil data. Some
predictions are possible from titration data but it is important that all data are
compatible, particularly the compositions of the STO and the flashed liquid and
the physical properties of pseudo components by matching to bubble point data
in both cases if you have them.
For this example we also had a measured precipitation point and you can see the
APEs resulting from the different approaches.
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 solids. To 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 the Coutinho model and the asphaltene
model is the standard Infochem model. The Combined Solids option is only
designed to look at solid formation, if you want to study more complex problems
such as hydrate inhibition you should choose the dedicated Hydrates model set.
If you only choose a single type of solid phase in the Combined Solids option
you will be asked to use the model for that type of solid instead, e.g. the hydrate
model if only hydrate phases are chosen.
Asphaltene precipitation
To understand what happens when more than one solid form a useful starting
point is to examine asphaltene precipitation 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:
The asphaltene model parameters are matched with a bubble point of 120F and
2650 psia and an asphaltene precipitation point of 120F and 8750 psia. The
predicted APE is plotted below (use the same strategy for plotting as described
in the asphaltene case study).
User Guide for Multiflash for Windows Case studies – Combined solids  287
Wax and Asphaltene precipitation
To see the effect of simultaneous wax and asphaltene precipitation we first need
to re-characterise the fluid with an n-paraffin distribution in order to apply the
Coutinho model. In the PVT form tick the box 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:
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.
288  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 slightly.
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 APE.
With water present use the phase envelope plotter to generate all the phase
boundaries. Starting point for the asphaltene boundary 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 lower
APE 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 precipitation occurring at higher temperatures.
290  Case studies – Combined solids User Guide for Multiflash for Windows
Of course with water present there is also the possibility of a separate water
phase.
If the fluid is flashed at 70F and 1750 psia Multiflash will predict the formation
of 6 phases; gas, hydrocarbon liquid, water, hydrate2, asphaltene 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 so many phases will be affected by
kinetic factors as well as the thermodynamic equilibrium.
Case studies – Excel
spreadsheets
Introduction
There are some problems that 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. By default, the
spreadsheets are stored in the same directory with the mfl files, i.e. under the tree
\Infochem\MF44\MFL Files from the Multiflash 4.4 installation on your
computer.
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.
User Guide for Multiflash for Windows Case studies – Excel spreadsheets  293
Notes
The first spreadsheet consists of notes on how to use UNFICAFIT.xls and how
to enter the fitted BIPs in Multiflash.
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 if you have it
 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 generated by the Multiflash functions when the calculation
in the spreadsheet is updated. It includes both 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 criterion for minimisation. The default setting is to
minimise the sum of squares of the differences between given and
predicted temperature or pressure. It is possible to minimise
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. To change this constraint use 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 “Units for BIPs
The BIPs for most equation of state methods, Wilson A, Regular Solution and
Flory Huggins are dimensionless. For other activity methods and the two CPA
association parameters the BIPs have associated units. The default units in
294  Case studies – Excel spreadsheets User Guide for Multiflash for Windows
Multiflash are J/mole. If BIPs from external sources are used in Multiflash it is
important that either the BIP units are changed to match the input values or the
numeric values of the BIPs are changed to J/mole.
The choice of units appears once the Units button is activated in the BIP display.
J/mol is the Multiflash standard for the dimensioned activity model BIPs.
cal/mol and K are the values used in the Dechema Data Series for activity model
VLE and LLE BIPs. The “Aspen” format allows you to transfer the BIP values
for the NRTL equation from Aspen Plus without further change.
The actual input functions for the activity BIPs are as follows:
In J/mol K Aij=a + bT + cT2
In cal/mol K Aij/4.184=a + bT + cT2
In K Aij/R=a + bT + cT2
Dimensionless Aij/RT=a + b/T + cT
Aspen format Aij/RT=a + b/T + cT
For the NRTL equation, the  parameter is defined as follows:
All formats except Aspen ij= a + bT + cT2
Aspen format ij= a + b(T-273.15) + c(T-273.15)2
Supplementing or overwriting BIPs” on page 59.
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.
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 points from the data available.
If you have less data then you should enter #N/A in the cells which would
otherwise be empty. 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 advised to enter #N/A for the y compositions. If you fail to do
this the Solver will still function provided the minimisation criterion is based on
difference in temperature or pressure, which is 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
Several of the engineers using the Multiflash GUI 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, which many engineers find useful and which we will still issue as
part of the implementation. Of course you will only be able to use any worksheet
if you have licensed the appropriate model.
The Solids.xls includes the recommended PVT analysis routines and solids
models; the CPA/Electrolyte model for Hydrates, the Coutinho wax model for
waxes and the asphaltene model is standard.
The spreadsheet consists of several worksheets and each worksheet has the
relevant models built-in in hidden rows or columns. As the PVT Analysis
procedure is complex, the PVT calculations are carried out using the Multiflash
GUI, and the mfl file written and referenced in the first worksheet.
The Excel calculations are set to manual using the Tools/Options or
Formulas/Calculation Options facility depending on the Excel's version. 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
The user characterises the PVT using the Multiflash GUI and enters the full
directory path and mfl file name to provide the characterised fluid information.
As all calculations in the spreadsheet have to be referenced to this fluid
characterisation we recommend that the characterisation is based on splitting the
fluid plus fraction from C6 into 15 pseudocomponents for both iso-paraffins and
n-paraffins. This controls the number of components and negates the need for the
user to modify the Excel functions to ensure that all components and
compositions are included in any calculation. The units for calculation are also
set in this worksheet.
This first worksheet includes a bubble point calculation at a temperature or
pressure set by the user. This allows you to decide whether to tune the petroleum
fraction properties to match a known bubble point or if this is unnecessary.
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.
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 precipitation, 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 predicts the wax appearance temperature (WAT)
without any further tuning plus the amount of wax formed at a user specified
T,P. The calculation is carried out based on the fixed wax phase fraction flash
function and the amount of wax is set to be .00015 mole fraction of wax in the
liquid+wax phases. There is a function called MF_PWAT, equivalent to the
WAT button in the GUI, which calculates the WAT at a fixed mass or mole
fraction of the wax phase. This can be relative to either the total fluid or to the
liquid plus wax phases.
For matching a measured WAT for a finite amount of wax phase, a command is
used for specifying the measured WAT in the Solids.xls. For the detailed
information about how to use the commands, refer to the section of Matching
wax data in the Multiflash Command Reference manual.
The WAT is plotted automatically as a function of pressure. The starting
pressure and step can be set by the user to obtain the pressure range of choice.
These calculations can be repeated based on matching to a known WAT, if one
is available.
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. The matching is done by using a command with the temperature and
pressure referred to either asphaltene ADE or reservoir condition. For detailed
command information, refer to the section on Matching asphaltene deposition
point in the Multiflash Command Reference manual.
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 precipitation envelope
automatically with starting points derived from the precipitation or reservoir
conditions. However, as the engineers using our Windows phase envelope
facility will appreciate it is difficult to make this absolutely fail-safe.
Asphaltene with gas injection
The effect of gas injection on asphaltene flocculation is perhaps most easily
calculated in Excel. The asphaltene model parameters for any fluid should be
retained when studying the effect of added gas. 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 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 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. The spreadsheet
predicts inhibitor amounts or concentrations required for hydrate inhibition at set
conditions.
Users who want to investigate hydrate behaviour only, may find the
hydrateinfo.xls and hydratecpa.xls spreadsheets useful. They have a restricted
component list (gases and gas condensates) but offer a choice of fluid and salt
model and a wider choice of calculations.
Case study – Mercury
partitioning
Introduction
This section is only applicable if your Multiflash license includes the mercury
model.
Infochem has developed a mercury model for prediction of the solubility of
mercury in natural gases and condensates, and the distribution of mercury
between gas, condensate and water phases. The mercury model is available in
combination with RKSA, PR78A or CPA-Infochem fluid models.
In condensates and petroleum liquids, organomercury compounds are significant
and may be the predominant form of mercury, although it is generally agreed
that mercury in natural gas is almost all in elemental form. Dimethylmercury and
diphenylmercury are chosen to represent light and heavy organomercury
compounds respectively. The mercury model in Multiflash is based on data for
the solubility both in hydrocarbons and in water, including data which is not
accessible in public domain.
The mercury model was originally developed based on the RKSA equation of
state. This is our recommendation for the fluid phase model. However PR78A
and CPA may be chosen for compatibility with fluid characterisation base on
these models.
Defining the mercury model

The mercury model may be defined by selecting the mercury tab in the
Select/Model Set box
The phases which can be defined for this model in the model selection form are
gas, liquid1 (hydrocarbon liquid), liquid2 (hydrocarbon liquid), water, liquidHg
(liquid mercury), solidHg (solid mercury), and ice. We recommend that you do
not define a second hydrocarbon liquid phase (liquid2) unless you anticipate the
possibility of multiple hydrocarbon liquid phases.
Calculating mercury partitioning and dropout

Once the mercury model has been defined the fluid components are defined
using Select/Components as usual and entering the fluid composition in the
Composition drop down menu. The example file for this case study is supplied
as Hg_Example.mfl, and uses RKSA as fluid model.
In this particular example we have only specified mercury but the principle is the
same if the components dimethyl- and diphenylmercury are present.
To demonstrate the partitioning we envision a simplified flowsheet where the

feed gas goes through a warm separator, the gas phase exiting this separator then
enters a cold separator and the exiting gas is compressed for export.
If the mercury model is used in an Excel spreadsheet or a third party simulator,
the streams can be set to be merged and recycled automatically but in the
Multiflash GUI it is only possible to use one stream composition as input at a
time for flash calculations.
Once Hg_Example.mfl has been loaded, enter the 4 degC and 77 bar of the warm
separator condition and carry out a PT flash.
As shown above, the mercury partitions among the fluid phases (Gas, Liquid1
and Water) .
To simulate the phase separation at the cold separator condition, the gas phase
composition can be highlighted, copied and then pasted into the Composition
drop down menu to provide the feed for the PT flash for the cold separator. The
conditions for the cold separator are set to -15 degC and 41 bar, and a new PT
flash is performed. These conditions correspond to having a choke between the
two separators, which reduces the pressure from 77 bar to 41 bar, resulting in the
temperature dropping to -15 degC.
At these conditions the separator is cold enough for a separate liquid mercury
phase to form. If the stream is cooled down even further, for example to -52
degC, then solid mercury will form instead and slightly more mercury drops out.
As can be seen from above, the mercury model can calculate mercury dropping
out either as a liquid or as a solid, and a flash calculation shows whether mercury
drops out at the given conditions. In Multiflash the fixed phase fraction flash
can be used to calculate the temperature or pressure at which a pure mercury
phase will start to drop out.
If the gas from the cold separator is compressed to 100 bar, such as for gas
export, then a fixed phase fraction flash at that pressure can be used to determine
the temperature at which mercury will start to drop out.
If we do the calculation for the gas output from the cold separator at -15 degC at
100 bar we can see that liquid mercury will begin to dropout at -8.7 degC.
If we use the cold separator at -52 degC and 41 bar instead, then mercury will
not dropout till the temperature is below -48 degC at 100 bar, at which point
solid mercury begins to form. This is because of the lower amount of mercury in
the gas stream from the cold separator at -52 degC compared to the gas stream
from the cold separator at -15 degC.
Other calculations
The mercury model can be used for any flash calculation such as P,S or P,H. The
model can also be used for mercury partitioning in a gas dehydrator.
TEG has been included in the component list for the example provided, but was
present at zero concentration. If the TEG is added, e.g. 0.3 moles, then the
calculations can be repeated but in this case starting with a simple dehydrator
flash at 10 degC and 110 bar. You can then see the mercury partitioning into the
aqueous TEG phase and the consequent effects.
Distribution of mercury species

As mentioned in the introduction, the mercury model in Multiflash can model
elemental mercury, dimethylmercury and diphenylmercury, but the model is not
able to predict how much of a measured total mercury content is elemental
mercury, and how much is organomercury.
For a given total mercury content in a gas stream it is reasonable to assume that
all the mercury is elemental mercury, as elemental mercury is much more
volatile than the two organomercury components.
However, if the measured total mercury content is for a separator liquid stream,
it is difficult to know exactly how much of each of the three mercury
components that corresponds to. Assuming all mercury is elemental might lead
to an over-prediction of the amount of mercury in the evolved gas phase when
the separator liquid is further processed.
One possible way of solving the problem is to assume some distribution between
the three mercury species in the separator liquid. (An equimolar distribution of
dimethylmercury and diphenylmercury can be assumed if no information is
available). If a measurement of the mercury content for the evolved gas phase is
available, the amount of elemental mercury in the assumed distribution for the
separator liquid can be adjusted to match the measurement for the gas phase.
This approach is not very accurate and is not based on observations, but it will
give the best possible estimate of the distribution of mercury between the species
based on the available information, and will agree with the mercury content in
both the separator liquid and the evolved gas.
Appendix - Multiflash
Commands
Introduction
The Multiflash command language is common to all Multiflash implementations
- 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 Multiflash GUI the use of commands has largely been replaced by the
menu choices and toolbar buttons. However, there are some Multiflash facilities
that are not available as menu/toolbar options so there are a few circumstances
when it is necessary to .make direct use of Multiflash commands.
Commands
From the Tools menu choose Command. A command window will be displayed.
You can then enter a command and either press <Enter> or click on the Send
command button to send the command to Multiflash.
The command shown in this example will provide details of the specified model,
including the name of the associated BIP dataset.
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
User Guide for Multiflash for Windows Appendix - Multiflash Commands  311
 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
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 in “Models and input
requirements” on page 74. Model_options are additional
keywords that describe model variants, references to other,
previously-defined, models or references to the source of binary
interaction parameters.
Many .mfl files are provided and will provide examples of how to set up a model
definition.
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. The last line below defines the enthalpy and entropy datum
point. If it is not included then the default (as shown below) will be taken.
Puredata infodata;
bipdata oilandgas infobips;
chardata infochar tbsoereide;
datum enthalpy compound entropy compound;
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.
312  Appendix - Multiflash Commands User Guide for Multiflash for Windows
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 name
H2O for water. However, Multiflash will still recognise the original format of
Key Water water;
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, temperature function, units, binary pair, values for BIPs;
The default names for the model bipsets are the model name followed by BIP
e.g. PRBIP
For example, A typical file of BIP data might be:
bipset PRBIP 1 constant eos none butane pentane 0.01 ;
bipset PRBIP 1 constant eos none pentane hexane 0.01 ;
bipset PRBIP 1 constant eos none hexane heptane 0.01 ;
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.
If you define the bipset incorrectly, e.g. if for butane pentane the temperature
function is defined as activity with units of J/mol, then a warning message will
appear when you try to use this with the PR equation
bipset PRBIP 1 constant activity J/mol butane
pentane 0.01 ;
*** ERROR 584 ***
Existing BIP set uses a different temperature
function
Some examples for other models are shown below:
bipset WILSONBIP2 2 constant activity j/mol acetone
water 6139 1450;
bipset NRTLBIP3 3 linear activity J/mol methanol
water .22 4.4e-3 .30 -6.6e-3 .003 0.0
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.
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, vapour and vapour
phase type, valid settings are: are synonyms.
condensed 2. condensed means a pure
gas solid phase.
hydrate 3. solidsolution means a
liquid mixed solid phase
solidsolution
vapour
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 “Solid
freeze-out model” on page 39, 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 “Phase ” on page 178.
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
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
Units 57, 294
BIP databank 60
BIP set
Names 55
BIPs
Index see Binary interaction parameters 53

BIPs and models 53
BIPs available in Multiflash 54
BIPs for CSMA and GERG mixing rule 59
Black Oil Analysis 101, 223
Blending method 128
Blending procedure 129
Bubble and dew point flashes 143
Bubble point 143
C
A
Calculate 17
About Multiflash 194
Calculating asphaltene precipitation conditions 272
Activity coefficient equations in Multiflash 37
Calculating mercury partitioning and dropout 304
Activity coefficient methods 37
Calculating the bubble point curve 206
Activity coefficient model for gas phase 9
Calculating the dew point curve 207
Activity coefficient models 6
Calculating the water dew point line 209
see Models 37
Calculating wax appearance temperature (WAT) 261
Activity coefficients 177
Calculating wax precipitation 264
Activity model worksheets 294
Calculation options 11
Activity Models 179, 180
Calculation output 175
Adding a component 69
Calculations 2, 19
Adding a user-defined component 72
see Flash calculations 141
Adding water to the system 209
Calculations with inhibitors 252
Adding, inserting, replacing and deleting components
Can hydrates form at given P and T ? 252
69
CAPE-OPEN 7
Additional calculations 20
CAPE-OPEN Interface 188
Advanced Equation of state options 31
Carbon Dioxide high-accuracy model 36
Amount of inhibitor required to suppress hydrates
Carry out a the flash calculation 199
255
Carry out an isenthalpic flash 21
Appendix - Multiflash Commands 3
Carrying out the flash calculation 23
Applicability 36
Case studies 3, 197, 205, 243
Aqueous phase labelling 178
Asphaltenes 51, 267
Asphaltene matching 270
Combined solids 287
Asphaltene precipitation 287
Delump 225
Asphaltene with gas injection 300
Getting Started 13
Asphaltenes 51, 267, 299
Hydrate formation and inhibition 243
Case study 51, 267
Phase equilibria 205
Defining Asphaltene model 51
Polymers 237
Model 43
Pure component data 197
ASTM D86 distillation 104
PVT Analysis 214
Azeotropes 235
Refrigerants 229
Wax 50, 260
B Change the composition 20
Change the pressure 20
Backup file 26
Changing units 170
Basic characterisation properties 109
Characterisation 99, 107
Benedict-Webb-Rubin-Starling (BWRS) equation of
Check for Updates 193
state 34
Choice of Analysis method 276
Benedict-Webb-Rubin-Starling model 34
Chung-Lee-Starling model 45
Binary interaction parameters 10, 53, 54, 55, 57, 58,
Chung-Lee-Starling thermal conductivity method 45
294
Clearing previous problems 21
Displaying values 55
Combined solids 287
Supplementing and overwriting BIPs 58
Combined Solids Model 52
Temperature dependence 54
User Guide for Multiflash for Windows Index  317

Commands 3, 311 Defining a mixture 65
Appendix 311 Defining a problem in Multiflash 18
Tools/Command option 311 Defining models 312
Component cannot be found 86 Defining petroleum fractions 109
Component list 91 Defining phase descriptors and key components 314
Components 2, 63, 65, 66, 67, 68, 69, 70, 84, 197 Defining the asphaltene model 268
Adding a component to a stream 69 Defining the components 21
Databanks 63 Defining the hydrate models 243
Deleting components from a stream 70 Defining the mercury model 303
DIPPR 63 Defining the models 22
Displaying pure component data 197 Defining the problem in Multiflash 197
Inserting a component in a stream 69 Defining the wax model 260
Maximum number in stream 65 Deleting components 70
Normal components 63 Deleting petroleum fractions 112
Properties of normal components 63 Delump
Replacing a component in a stream 70 Case study 225
Selecting by formula 68 Delumping tool 113
Selecting by name 66 Delumping tool - Case study 225
Selecting by scrolling through list 66 Dew point 143
Selecting by substring 68 Differences between the PR Model in Multiflash and
Selecting components 66 Aspen Hysys 60
Synonyms of components 67 Diffusion coefficient 46
Troubleshooting 84 Diffusion coefficients 46
User defined 72 DIPPR 7, 63
Compositions 14, 23, 137, 171 Displaying status for current settings 181
Amounts and fractions 138, 170, 171, 176 Distillation curves 102
Specifying compositions 137 Distribution of mercury species 308
Conditions 14, 137, 139 Document Organisation 2
Conditions section of main window 137 Dortmund Modified UNIFAC method 38
Specifying compositions 137 Dortmund Modified UNIFAC model 38
Specifying enthalpy 139
Specifying entropy 139 E
Specifying internal energy 139
Specifying pressure 138 Edit 15
Specifying temperature 138 Editing petroleum fraction data 112
Specifying volume 138 Electrolyte model 81
Troubleshooting 139 Enter a composition for the stream 199
Consider all types of solution 167 Entering BIPs 232
Constants 73 Entering petroleum fractions 110
Co-Polymers 239 Enthalpy
Corresponding states (CSMA) model 35 Specifying for isenthalpic flash 139
CPA model CPA 10 Enthalpy definition 178
CSMA Entropy
Reference fluids 35 Specifying for isentropic flash 139
CSMA model 9 Entropy definition 180
Cubic plus association (CPA) model 32 Equation of state models 30
Current settings Equations of State Models 30
Display 181 Equations of state provided in Multiflash 30
Customising the phase envelope plot 155 Errors 176, 181
Convergence 176
Messages 181
D
Troubleshooting 52, 60, 84, 139, 165, 171, 181
Data Availability 277 Errors and warning messages 181
Data input 237 Estimated n-paraffin distribution 108
Databank not found 84 Eutectics 236
Databank not licensed 85 Example for blending 130
Databanks 7, 10 Example with asphaltenic crudes 133
DIPPR 63 Example with waxy crudes 132
INFODATA 63 Examples
Default units 169 Case studies 50, 51, 197, 205, 243, 260, 267, 303
318  Index User Guide for Multiflash for Windows

Getting Started 13 H
Excel interface 7, 202
Exiting Multiflash 27 Hayduk Minhas method 46
Hayduk-Minhas method 46
Help 191
F HELP 3, 17
File 14 Help Topics 191
Files High accuracy reference eos for water-ammonia
Loading problem setup files 18 binary system 6
OLGA PVT file 184 How to change a model 48
Output file 173, 174 How to Enter Multiflash Commands 311
PIPESIM PVT file 183 How to exit the program 27
Problem setup (mfl) files 18, 25, 26 How to specify models in Multiflash 47
Prosper PVT file 187 How to use the delumping utility 114
Saving a problem setup file 25 Huron-Vidal-Pedersen mixing rule 5
Saving results in an output file 27 Hydrate
Fitting the vapour pressure curve 31 Inhibitor Calculator 79
Fixed phase fraction flash 144 Nucleation model 41, 49, 245
Fixed phase fraction flashes 144 Hydrate calculations 159
Flash calculations 10, 139, 141 Hydrate calculations with Multiflash 246
Bubble points 143 Hydrate dissociation pressure at a given temperature
Definition of a flash calculation 141 254
Dew point 143 Hydrate dissociation temperature at a given pressure
Fixed phase fraction flash 144 254
Isenthalpic flash 143 Hydrate formation and dissociation pressure at given
Isentropic flash 143 temperature 250
Isochoric flash 143 Hydrate formation and dissociation temperature at
Isothermal (P,T) flash 142 given pressure 247
List of available flash calculations 142 Hydrate formation temperature at given pressure 249
Retrograde flash calculations 147 Hydrate inhibitors 79
Troubleshooting 165 Hydrate model 39, 244
Type of solution 147 Hydrate models 11
Flashes available in Multiflash 142 Hydrate phase boundary 251, 254
Flory Huggins model 38 Hydrates 39, 48, 243, 255, 301
Flory-Huggins 38 Case study 243
Fluid amounts 129 Hydrate inhibition case study 255
Fluid file name 128 Hydrate inhibitor model 42
Fluid Identification 14 Hydrate model 39
Fluid phase model 244 Phase boundary 251
Font 174 Hydrates in water sub-saturated systems 41
Fonts 182 Hydrates, Waxes and Asphaltenes 289
Frame Tab 152
Fugacity coefficients 177 I
Fuller method 46
Fuller model 46 IAPWS-95 35
Ice model 245
Ideal gas equation of state 30
G Ideal solution model 37
Gas and liquid Enthalpy based on saturated liquid Including a petroleum fraction 210
heat capacity 180 INFODATA 7, 10
Gas injection 282 Infochem fluids databank 63
Gas phase models for activity coefficient methods 38 Inhibition
GERG model 36 Hydrate inhibition case study 255
GERG-2008 36 Model for hydrate inhibition 42
GERG-2008 (Infochem extension) 36 Inhibitor calculator
Getting Started 2, 13, 205 alcohols/glycols 79
Groups not available for UNIFAC model 52 Inhibitor Calculator 6, 11, 79
Inhibitor modelling 42
Initial Values Tab 151
Input conditions
see Conditions 137

Input Conditions 2 M
Input data 102, 267
Input files Macleod-Sugden 2-phase variant (MCSA). 46
Loading a problem setup file 18 Macleod-Sugden method (MCS). 46
Problem setup files 18, 25, 26 Macleod-Sugden model 46
Saving a problem set up file 25 Manipulating the Output 177
Input section 14 Mass fraction flash 144
Inserting a component 69 Match bubble point 297
Installation 3 Matching 116, 122, 123, 128
Interface to other programs 141, 202, 235 Asphaltene flocculation 281
Excel spreadsheet 141, 202, 235 Dew and bubble points 116, 122, 128
Interfaces 7 Liquid viscosity 125, 126
Internal energy Wax Appearance Temperature 123
specifying as a flash condition 139 Matching Density/Volume 122
Introduction 1, 5, 9, 29, 63, 89, 137, 141, 169, 173, Matching dew and bubble points 116
183, 191, 197, 205, 243, 260, 267, 287, 293, Matching liquid viscosity 125
303, 311 Matching to asphaltene deposition data 281
ISAPWS-95 35 Matching using petroleum fraction properties 116
Isenthalpic flashes 143 Matching vapour viscosity 126
Isentropic flashes 143 Matching wax data/WAT 123
Isochoric flashes 143 Maximum water content allowable before hydrate
Isothermal (P,T) flash 142 dissociation 251
Menu options 14
Mercury 9
J mfl files 18, 25, 26
Joule-Thompson coefficient 12 Mixing rules 31
Liquid thermal conductivity 45
Liquid viscosity 45
K Surface tension 46
Key components 145, 314 Vapour thermal conductivity 46
Vapour viscosity 45
Model definition 129
L Model is not available 52
LBC 5 Modelling a polar mixture 230
LBC viscosity model 10 Modelling asphaltene flocculation 43
Lee-Kesler (LK) and Lee-Kesler-Plöcker (LKP) Modelling hydrate formation and inhibition 39
equations of state 34 Modelling wax precipitation 42
Lee-Kesler-Plöcker (LKP) model 34 Models 2, 5, 9, 22, 29, 37, 48, 53
Limit the number of phases 167 Advanced equations of state 31
Linear Gradient Theory 46 Asphaltenes 43
Linear Gradient Theory model 46 Benedict-Webb-Rubin-Starling (BWRS) 34
Liquid dropout and Wax precipitation curve 11 Binary interaction parameters (BIPs) 53
Liquid dropout curve calculation 158 Chung-Lee-Starling 45
Liquid enthalpy based on saturated liquid heat Corresponding states (CSMA) 35
capacity 179 COSTALD model 43
Liquid thermal conductivity mixing rule 45 Cubic plus association (CPA) 32
Liquid viscosity mixing rule 45 Diffusion coefficients 46
Liquid-liquid equilibria 234 Dortmund Modified UNIFAC 38
Loading a existing MFL file 26 Flory Huggins 38
Loading a model from a .mfl file 48 Fuller model 46
Loading a problem setup file 18 Gas phase models 38
Loading an existing problem file 18 GERG model 36
Loading files Hayduk Minhas method 46
Loading problem setup files 18 Hydrate model 39
Log file 27, 173, 174 Hydrate nucleation model 41, 49, 245
Saving the log file 27 IAPWS-95 35
Lohrentz-Bray-Clark model 44 Ideal gas 30
Lohrenz-Bray-Clark method 44 Ideal solution 37
Lee-Kesler-Plöcker (LKP) 34
Linear Gradient Theory 46
Liquid density model 43

Lohrentz-Bray-Clark 44 Multi-reference fluid corresponding states (CSMA)
Macleod-Sugden 46 model 35
Mixing rules 31
Model definitions 29 N
NRTL 37
Pedersen 44 New Features 5, 9
Peneloux density correction 31 New Features and Changes in Version 4.2 2
Peng Robinson (PR) 30 New Features and Changes in Version 4.4 and 4.3 2
PSRK 32 New high accuracy reference eos 6
Redlich-Kwong (RK) 31 New icon for Asphaltene precipitation curve 11
Redlich-Kwong-Soave (RKS) 31 No information on the amount of asphaltene in the oil
Regular Solution 38 278
Selecting model set 22 No reservoir or precipitation conditions 280
Selecting new model 48 No reservoir pressure 279
Solid models 39 No resin - asphaltene ratio 279
SuperTRAPP 45 Normal components 63
Surface tension 46 DIPPR 63
Surface Tension 46 INFODATA 63
Transport property 44 Properties of normal components 63
Troubleshooting 52 Notes 294
Twu 44 n-Paraffin distribution 105
UNIFAC 38 NRTL equation 37
UNIQUAC 37 NRTL model 37
Viscosity 44 Nucleation 248
Wax 42 Nucleation model 41, 49, 245
When to use activity methods 38
When to use BWRS 34 O
When to use CPA 32
When to use CSMA 36 Obtaining properties from the Pure Component Data
When to use cubic equations of state 32 option 200
When to use equation of state methods 30 Oil and gas systems 205
When to use LKP 34 OLGA 184
When to use PSRK 32 PVT file 184
When to use ZJ model 33 OLGA hydrate file 186
Wilson E 37 OLGA tables 7, 12
ZJ (Zudkevitch-Joffe) model 33 OLGA wax file 186
Models and input requirements 74 On-line help 191, 194
Models for solid phases 39, 48 Other calculations 24, 308
Models tab 6 Other flash calculations 212
Molecular weight and specific gravity 95 Other flash calculations with hydrates 251
Multiflash Other properties 110
Calculations 142 Other thermodynamic models 43
Case studies 197 Output 3, 27, 173, 174
Conditions 137 Enthalpy datum 178
Exiting the program 27 Entropy datum 180
Getting Started 13 Level of physical property output 164
Interfaces to other programs 183 Phase Identification 178
Models 29 Saving the output file 27
Output 173 Troubleshooting 181
Overview 1 Writing the results to a file 173, 174
Software system 1
Starting the program 13 P
Units 169
Multiflash Error Codes 193 PC-SAFT equation of state 33
Multiflash Excel Interface 12 Pedersen Model 44
Multiflash main window 13 Peng-Robinson (PR) model 30
Multiflash Main Window 13 Peng-Robinson 1978 (PR78) equation of state 31
Multiflash phase equilibrium algorithm 10 Peng-Robinson equation of state 30
Multiflash Software System 1 Performance enhancements 6
Petroleum Fluid Blending 127

Petroleum fluid composition 94 Physical property databanks 63
Petroleum Fluids 2 Properties of normal components 63
Petroleum Fraction Input Table 7 Property output in Multiflash 164
Petroleum fractions 63, 109, 112, 113 Prosper
Defining petroleum fractions 109 PVT file 187
Deleting petroleum fractions 112 Prosper PVT files 187
Editing petroleum fraction data 112 Provide a key component 168
Importing characterised petroleum fractions 109, Provide a starting estimate 167
210 Pseudocomponents 98
Troubleshooting 113 PSRK equation of state 32
Petroleum Fractions 65 PSRK model 32
Phase descriptors 313 Pure solid phase 49
Phase diagram 147 PVT Analysis 11, 89, 101, 214, 296
Phase envelope 24, 148, 166, 208 Case study 214
Customising 155 n-paraffins 105
Phase envelope output 154 Saving an analysis 101
Phase Envelopes 148 Troubleshooting 109
Phase Envelopes for solids 11, 157 PVT Lab Analysis input 89
Phase key components 6 PVT Lab Analysis input with n-paraffin analysis 105
Phase labelling 178, 182 PVTSim CHC file import tool 189
Phase names 144 PVTSim import tool 6, 11
Phase tab 149
Phases 39, 144, 147, 166, 182, 245, 313 R
Example of a phase diagram 147
Example of a phase envelope 166 Redlich-Kwong (RK) and Redlich-Kwong-Soave
Phase descriptors 313 (RKS) equations 31
Phase labels 182 Redlich-Kwong (RK) model 31
Phase names 144, 182 Redlich-Kwong-Soave (RKS) model 31
Phase types 144 Reference fluids 35
Selecting phases 47 Refrigerant mixtures 229
Solid phases 39 Refrigerants
Physical properties of a pure component 197 Case study 229
PIPESIM Regular Solution model 38
PVT file 183 Regular Solution theory 38
Pipesim PVT files 183 Reid vapour pressure 11, 162
Plot the phase envelope 166 Reid Vapour Pressure 162
Plots Replacing a component 70
H, S, U, V phase boundaries 148 Results 14, 19, 26, 27, 173
Phase envelope 148 Level of physical property output 164
Polar systems 230 Printing the results 14, 26
Polymers 237 Results window 173
Case study 237 Saving the results in a file 14, 27
Poynting correction 9 Results window 14
PRA 10 Retrograde 147
Presence of water 109 Retrograde condensation 147
Pressure Retrograde dew point 147
Specifying as an input condition 138 Retrograde Dew Point 11
Pressure and temperature 23 RKSA 10
Printing RKSA-Info, CPA and PR 10
Output 26 Running Multiflash 2
Printing the output 26, 175
Problem setup file 25 S
Loading a problem setup file 18
Saving a problem setup file 25 Salt calculator 81
Problem setup files 18, 26 Salt component 5
Problems defining a petroleum fraction 113 Salt inhibition 256
Problems when matching 127 SARA Analysis 97
Properties Saturation P at reservoir T 272
Displaying pure component properties 197 Saving a PVT Analysis 101
Level of physical property output 164 Saving files

Saving a problem setup file 25 PSF file for HTFS programs 183
Saving results PVT file for PIPESIM 183
Writing the results to a file 173, 174 TBP curves 221
Saving the output 27 TBP distillation 102
Saving the problem setup 25 Technical support 28, 194
Scale model 245 Temperature
Scale precipitation 258 Specifying as an input condition 138
Scaling and general freeze-out model 39 Temperature dependence of BIPs 54
Searching for components Temperature-dependent properties 73
By formula 68 The basis of a flash calculation 141
By name 66 The Multiflash GUI 1
By scrolling through list 66 The output does not include everything expected 181
By substring 68 The Peneloux density correction 31
Identifying synonyms 67 The results 19
Select 15 The results window 173
Select components by formula 68 The Toolbar 18
Select components by name 66 Thermal conductivity 45
Select components by scrolling through a list 66 Models 45
Select components by substring 68 Titration 283
Selecting components 66 To generate the file 187
Sensitivity of calculations to variation in input data To specify the Ideal Mixing model set: 197
276 Tolerance calculations 161
Sensitivity to characterisation 109 Too many components in the mixture 87
Set Input Conditions 23 Tools 16
Setting up a new problem 21 Total amount of fluid 96
Setting up preferred models in Multiflash 48 Total Wax Content 97
Show functions 181 Transport properties
Soave-Redlich-Kwong (RKS) model 31 Displaying transport property values 164
Solid freeze-out model 39 Models 44
Solids.xls 296 Surface tension 46
Specific gravity conversion 95 Thermal conductivity 45
Specify the pure component of interest 198 Viscosity 44
Specifying compositions 137 Transport property models 44
Specifying data for a user-defined component 73 Troubleshooting 52, 60, 84, 109, 139, 165, 171, 181
Specifying enthalpy, entropy and internal energy 139 Binary interaction parameters 60
Specifying temperature, pressure and volume 138 Calculations 165
Specifying the data source 66 Components 84
Specifying the physical property output level 198 Models 52
Stability analysis 176 Output 181
Starting estimate for flash calculations 167 PVT Analysis 109
Starting Multiflash 13 Units 171
Stream types 76 Troubleshooting - BIPs 60
SuperTRAPP model 44, 45 Troubleshooting - components 84
SuperTRAPP thermal conductivity method 45 Troubleshooting - flash calculations 165
SuperTRAPP Viscosity Model 44 Troubleshooting - input conditions 139
Supplementing or overwriting BIPs 58 Troubleshooting - models 52
Supplying an external file of BIPs 313 Troubleshooting - output 181
Surface tension 7, 46 Troubleshooting - PVT Analysis 109
Models 46 Troubleshooting - units 171
Surface tension mixing rule 46 Tutorial 13
Sutton Model for surface tension. 5 Twu Model 44
Synonyms 67
Component synonyms 67 U
UNFACFIT.xls 293
T
UNIFAC 294
Table 17 UNIFAC method 38
Tables 7, 12 UNIFAC model 38
Tabular output 141, 183 UNIQUAC 37
Excel interface 141 UNIQUAC equation 37

Units 3, 57, 60, 169, 170, 171, 294 When to use the BWRS equation 34
Default units 169 When to use ZJ model 33
Selecting units 170 When you may need to use commands 311
Troubleshooting 171 Will hydrates form at given P and T ? 246
Units for BIPs 57, 60, 294 Wilson A equation 37
Units for BIPs 57 Wilson E equation 37
Updates 5, 9 Wilson E model 37
Usability 12 Windows GUI 6, 11
Use the P,T flash 166 Writing the results to a file 174
User defined carbon number cuts 219
User defined components 72 Z
User Defined Cuts 100
User-defined components 72 ZJ (Zudkevitch-Joffe) model 33
Using INFOBIPS 230
Using the fixed phase flash 146
Using the menu 47
V
Vapour thermal conductivity mixing rule 46
Vapour viscosity mixing rule 45
Vapour-liquid-liquid equilibria 235
Viewing and editing pure component data 70
Viewing BIP values 55
Viscosity 44
Matching liquid viscosity 125, 126
Models 44
VLEAutoPlot 149
VLEFIT.xls 295
Volume
Specifying as a flash condition 138
Volume fraction flash 144
W
Warning option for matching and PVT form 26
Warnings 176, 181, 234
Additional phases 234
Convergence 176
Water cut 97
Water-Ammonia 35
Wax 260, 298
Case study 50, 260
Coutinho Model 42
Defining Wax model 50
Matching WAT 123
Wax and Asphaltene precipitation 288
Wax Appearance Temperature 159
Wax calculations 159
Wax Precipitation Curve 160
Waxes 50
What is a model? 29
What the model definition means 312
What types of model are available? 29
When to use activity coefficient models 38
When to use CPA. 32
When to use cubic equations of state 32
When to use equation of state methods 30
When to use LK or LKP 34
When to use PSRK 32

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User Guide for

Multiflash for Windows

Infochem/KBC Advanced Technologies plc

Infochem/KBC Advanced Technologies plc

New Features and Changes in Version 4.4 and 4.3 5

New Features and Changes in Version 4.2 9

User Guide for Multiflash for Windows Contents  iii

iv  Contents User Guide for Multiflash for Windows

User Guide for Multiflash for Windows Contents  v

vi  Contents User Guide for Multiflash for Windows

Input conditions 137

User Guide for Multiflash for Windows Contents  vii

Interfaces with other programs 183

Case studies - Pure component data 197

Case studies - Phase equilibria 205

viii  Contents User Guide for Multiflash for Windows

Case studies - Hydrate dissociation, formation and inhibition 243

Case studies – Wax precipitation 260

Case studies – Asphaltene flocculation 267

User Guide for Multiflash for Windows Contents  ix

Case studies – Combined solids 287

Case studies – Excel spreadsheets 293

Case study – Mercury partitioning 303

Appendix - Multiflash Commands 311

x  Contents User Guide for Multiflash for Windows

The Multiflash GUI

Multiflash Software System

User Guide for Multiflash for Windows Overview  1

New Features and Changes in Version 4.4 and

New Features and Changes in Version 4.2

2  Overview User Guide for Multiflash for Windows

Appendix - Multiflash Commands

User Guide for Multiflash for Windows Overview  3

Huron-Vidal-Pedersen mixing rule

Sutton Model for surface tension.

New high accuracy reference eos

Activity Coefficient models

Phase key components

PVTSim import tool

Petroleum Fraction Input Table

Activity coefficient model for gas phase

Binary Interaction Parameters

CPA model CPA

RKSA-Info, CPA and PR

Multiflash phase equilibrium algorithm

PVTSim import tool

Reid vapour pressure

Liquid dropout and Wax precipitation curve

New icon for Asphaltene precipitation curve

Phase envelopes for solids

Retrograde Dew Point

Multiflash Excel Interface

Multiflash Main Window

User Guide for Multiflash for Windows Getting Started  13

14  Getting Started User Guide for Multiflash for Windows

User Guide for Multiflash for Windows Getting Started  15

16  Getting Started User Guide for Multiflash for Windows

See “Interfaces with other programs” on page 183.

User Guide for Multiflash for Windows Getting Started  17

Defining a problem in Multiflash

Loading an existing problem file

Loading a problem setup file

This will display the file selection dialogue