Beruflich Dokumente
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Version 4.4
February 2014
This User Guide and the information contained within is the copyright of Infochem Computer Services Ltd.
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
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
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
Introduction ............................................................................................................................... 9
Models ....................................................................................................................................... 9
CSMA model............................................................................................................... 9
Mercury ....................................................................................................................... 9
Poynting correction ..................................................................................................... 9
Activity coefficient model for gas phase ..................................................................... 9
LBC viscosity model ................................................................................................. 10
Contents iii
Getting Started
13
Models
29
Introduction ............................................................................................................................. 29
What is a model? ..................................................................................................................... 29
What types of model are available? ......................................................................................... 29
iv Contents
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
Input conditions
137
Calculations
141
Units
169
Introduction ........................................................................................................................... 169
Default units .......................................................................................................................... 169
Changing units ....................................................................................................................... 170
Troubleshooting - units.......................................................................................................... 171
Contents vii
Output
173
183
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
197
205
viii Contents
243
260
267
Contents ix
287
293
303
311
Index
x Contents
317
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.
Overview 1
Document Organisation
The rest of this document is divided into the following sections.
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
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.
Installation
Information on how to install Multiflash software is provided in the separate
Installation Guide for Multiflash for Windows.
Overview 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.
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 RKSAInfochem.
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.
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.
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.
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.
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.
RKSA
O2+H2O
PRA
O2+n-octane
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 SO4have been
added to the INFODATA databank.
Windows GUI
PVTSim import tool
It is now possible to import characterised fluids from PVTSim if they were
exported to a CHC file.
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.
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.
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.
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.
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
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.
Getting Started 15
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
16 Getting Started
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.
Help
The HELP menu enables you to get help on a variety of topics, see Help on
page 191.
Getting Started 17
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.
Or
Click on the Load Problem Setup button
on the toolbar.
18 Getting Started
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
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.
Getting Started 19
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:
2.
3.
20 Getting Started
2.
2.
Data sources
Models
Components
Compositions
Input conditions
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 dropdown 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.
Getting Started 21
Choose the components needed for the problem, in this case butane and pentane
as follows:
1.
2.
3.
Click on the Close button, this will return you to the Main
Window.
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.
22 Getting Started
Click on OK and then Close the Select Model set dialogue to return to 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.
Getting Started 23
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
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.
24 Getting Started
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).
, 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.
Getting Started 25
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.
26 Getting Started
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.
Getting Started 27
Technical support
For contact information see Technical support on page 194.
28 Getting Started
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.
fiv fil
v
f i l is the
Models 29
30 Models
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.
Models 31
32 Models
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.
Models 33
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.
34 Models
Reference fluids
The following substances are included in the model:
acetone
ammonia
argon
fluorine
helium
heptane
benzene
iso-butane
n-butane
1-butene
iso-butene
cis-2-butene
trans-2-butene
carbon dioxide
carbon monoxide
carbonyl sulphide
decane
DME
dodecane
ethane
ethanol
ethylene
cyclohexane
iso-hexane
n-hexane
hydrogen
hydrogen sulphide
krypton
methane
methanol
neon
nitrogen
nitrogen trifluoride
nonane
octane
oxygen
iso-pentane
neo-pentane
n-pentane
propane
propylene
sulphur
dioxide
SF6
toluene
water
xenon
R11
R113
R114
R115
R116
R12
R123
R1234YF
R1234ZE
R124
R125
R13
R134A
R14
R141B
R142B
R143A
R152A
R161
R218
R22
R227EA
R23
R236EA
R236FA
R245FA
R32
R365MFC
R41
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 singlephase regions are 0.3% for the density and 200 J / mol for enthalpies.
Models 35
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
nitrogen
CO2
ethane
propane
n-butane
iso-butane
n-pentane
iso-pentane
hexane
heptane
octane
nonane
decane
argon
oxygen
hydrogen
CO2
water
helium
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.
36 Models
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.
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 liquidliquid 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 vapourliquid-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 vapourliquid-liquid calculations. There are UNIQUAC VLE and LLE variants as for the
Models 37
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.
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.
38 Models
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.
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
Models 39
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.
40 Models
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.
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:
Models 41
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 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.
42 Models
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 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.
Models 43
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.
44 Models
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.
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.
Models 45
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).
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.
46 Models
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.
Models 47
48 Models
The fluid model used in conjunction with the solid phase hydrate model is CPAInfochem. 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.
Models 49
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.
50 Models
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.
Models 51
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.
52 Models
-13201 ***
Models 53
54 Models
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.
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
TEMPERATURE FUNCTION: EOS
0.5055762
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
Models 55
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.
56 Models
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.
Models 57
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
58 Models
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 dont 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 ***
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.
Models 59
Troubleshooting - BIPs
Units
Reference:
Dechema Chemistry Data
Series (CDS)
ISSN 0840-9645
Volume I to XVI
Publisher: Dechema
We cannot stress often enough that to obtain correct results the BIPs entered
must match the Multiflash definition and be in the correct units. A very good
source of phase equilibrium data and BIPs is the Dechema Chemistry Data
Series which is in several volumes. It is useful to note that their standard
convention is to report activity model BIPs for VLE in cal/mol. Either these
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.
60 Models
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.
Models 61
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.
Components 63
64 Components
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
Components 65
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.
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
66 Components
The component may then be selected for use in Multiflash either by doubleclicking 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).
Components 67
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.
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.
68 Components
names ending in methane and *methane* finds all names containing methane.
Entering methane alone searches for an exact match.
Adding a component
Components are added to the selected list for a mixture as described earlier, by:
By pressing the <Enter> key after entering a name in the text box
(with Name option button selected).
If you try to add the same component twice you will be warned, for example,
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:
Components 69
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.
70 Components
Components 71
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.
72 Components
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.
Components 73
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.
molecular weight,
critical temperature,
critical pressure,
acentric factor
The following table lists the data required in addition to the above for each
model.
74 Components
Model
Thermodynamic
RKS
RKSAPI
RKSA
RKSAINFO
RKS-HVP
PR, PR78
PR-HVP
PRA, PR78A
PSRK
LK, LKP
BWRS
CSMA or GERG-2008
CPA
PC-SAFT
Ideal mixing
NRTL
Wilson E
UNIQUAC
UNIFAC
Dortmund Modified
UNIFAC
Regular Solution
Flory-Huggins
Perfect gas
RK
Hayden OConnell
Hydrate
Wax
Asphaltene
Mercury partitioning
model
Components 75
Transport properties
Pedersen
Twu
LBC
Lohrenz-Bray-Clarke
CLS
Chung-Lee-Starling
SuperTRAPP models
Macleod-Sugden (MCS
and MCSA)
Costald
Liquid viscosity mixing
rule
Vapour viscosity mixing
rule
Liquid thermal
conductivity mixing rule
Vapour thermal
conductivity mixing rule
Surface tension mixing
rule
Linear Gradient Theory
Diffusivity Fuller's
method
Diffusivity - HaydukMinhas method
None
boiling point (TBOIL), vapour pressure,
saturated liquid density
critical volume (VCRIT), or model specific VC
(VCLBC), specific gravity (SG), dipole moment
(DIPOLEMOMENT)
critical volume (VCRIT), dipole moment
(DIPOLEMOMENT)
critical volume (VCRIT), dipole moment
(DIPOLEMOMENT)
parachor (PARACHOR)
saturated liquid density
liquid viscosity
vapour viscosity
liquid thermal conductivity
vapour thermal conductivity
surface tension
Saturated liquid surface tension (STENSION)
chemical formula (FORMULA), UNIFAC
subgroup structures (UNIFAC).
critical molar volume (VCRIT), normal boiling
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.
76 Components
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.
Components 77
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
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.
78 Components
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.
Components 79
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 60F). 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.
80 Components
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
modelPure 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:
Components 81
82 Components
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.
Components 83
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.
84 Components
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.
Components 85
If you have an earlier version of DIPPR and try to run Multiflash with the latest
version, then following error message will appear.
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
86 Components
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.
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.
Components 87
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:
Petroleum fluids 89
and the normal boiling point of n-nonane + 0.5C. 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
H2
Reservoir Fluid
Mole %
Weight %
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
Benzene
Cyclo-hexane
1.60
0.24
2.12
0.75
0.11
1.00
0.60
0.09
0.91
1.01
0.16
1.41
0.88
0.12
1.22
C7
C8
C9
Heptanes
6.27
3.51
1.13
3.25
3.35
Me-Cyclo-hexane
Toluene
3.76
1.54
2.07
0.79
0.61
0.22
1.91
0.76
1.93
0.72
Octanes
7.57
4.85
0.54
3.44
4.05
Ethyl-benzene
Meta/Para-xylene
Ortho-xylene
0.59
1.97
0.72
0.35
1.17
0.43
0.03
0.07
0.02
0.26
0.85
0.31
0.29
0.93
0.34
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
_____
100.00
10.88
_____
100.00
0.00
_____
100.00
1.29
_____
100.00
8.26
_____
100.00
Totals:
C36+
Molecular Weight (g mol-1)
Density at 60F (g cm-3)
90 Petroleum fluids
Flashed Liquid
Flashed Gas
Mole %
Weight %
Mole %
625
0.9925
button or the
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:
Petroleum fluids 91
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.
92 Petroleum fluids
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 fluids 93
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
94 Petroleum fluids
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.
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 60F 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.
Petroleum fluids 95
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.
96 Petroleum fluids
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 F, 1 atm).
You should note the following points
The procedure used is approximate but does allow for loss of water
to the vapour phase.
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.
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.
Petroleum fluids 97
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.
98 Petroleum fluids
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
Petroleum fluids 99
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.
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.
Input data
The minimum data required are:
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%.
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.
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.
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 nparaffin 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 nparaffin 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 nparaffin. 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 nparaffin and non-n-paraffin pseudocomponents is displayed in the main window.
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.
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
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.
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.
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.
. The following
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:
The fluid is ready to be delumped. Click the Delump button. The resulting
fluid is displayed in the Current Fluid table.
NOTE:
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.
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
15P
16P
17P
18P
19P
20P
21P
22P
23P
24P
EXPERIMENTAL AND CALCULATED VALUES: VOLUME
T(exp)/K
P(exp)/bar
381.15
360.
381.15
350.
381.15
340.
381.15
330.
350.
100.
350.
80.
350.
60.
350.
40.
0.00261675
0.00283127
0.00309332
0.00328365
0.00353665
0.00387479
0.0042509
0.0047303
0.00514017
0.00526666
0.00557851
Vol(exp)/kg/m3
262.375
258.229
253.93
249.228
93.
73.
55.
35.
-6.57719E-6
-7.11674E-6
-7.77269E-6
-8.24893E-6
-8.88117E-6
-9.72486E-6
-1.06627E-5
-1.18573E-5
-1.28798E-5
-1.31955E-5
-1.39722E-5
Vol(cal)/kg/m3
263.20947
258.47254
253.59631
248.57439
94.583391
73.892152
53.908961
34.831117
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 nparaffin pseudo-components as it is these which form the wax phase.
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.
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.
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 pseudocomponents 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 pseudocomponents 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 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.
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.
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.
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.
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 substream 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,
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.
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
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.
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.
Temperature (T)
Pressure (P)
Volume (V)
Enthalpy (H)
Entropy (S)
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
Calculations 141
Isothermal flash
P,H flash
T,H flash
H,S flash
P,V flash
S,V flash
T,V flash
U,V flash
P,U flash
T,U flash
T, Retrograde dew
point
P, Bubble point
T, Bubble point
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.
142 Calculations
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
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
description on page 148.
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
description on page 148.
Calculations 143
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
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
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
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
144 Calculations
vapour phase
LIQUID1
LIQUID2
WATER
ICE
HYDRATE1
HYDRATE2
HYDRATEH
WAX
wax phase
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
Calculations 145
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.
or fixed temperature
146 Calculations
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.
Calculations 147
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 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:
148 Calculations
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
Calculations 149
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.
150 Calculations
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.
Calculations 151
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.
152 Calculations
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.
Calculations 153
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.
154 Calculations
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.
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.
Calculations 155
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.
156 Calculations
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.
Calculations 157
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.
158 Calculations
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.
Calculations 159
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.
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.
T (degC)
0.
4.
8.
12.
16.
20.
24.
28.
160 Calculations
bar
32.
36.
40.
44.
48.
52.
56.
60.
64.
66.40
0.725042
0.525915
0.377582
0.271559
0.195085
0.131349
0.0696203
0.0172402
0.00132507
0.
The starting temperature is 0C, 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.
Calculations 161
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..
162 Calculations
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).
Calculations 163
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
164 Calculations
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.
Calculations 165
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:
166 Calculations
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.
Calculations 167
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.
168 Calculations
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.
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
170 Units
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.
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 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
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.
174 Output
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.
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
Output 175
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
the stability of a solution with
respect to the formation of
another phase of a type
already specified. For
example, if you have only
defined two liquid phases the
possible formation of a
vapour or solid cannot be
checked
STABLE means that no further phases (out of the list provided) will form.
Sometimes a solution may be labelled as UNSTABLE, meaning that further
phases would form if more phases were allowed for in the problem setup. An
example might be if only vapour and one liquid phase are specified but in fact
the true solution is vapour-liquid-liquid. If you want to look for the extra phase
then you must include an additional phase descriptor in your model definition.
If, however, you are at very low temperatures you may be looking at a
metastable solution and wish to retain only the number of phase descriptors
already defined. The results of a hydrate nucleation calculation will always be
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.
176 Output
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
BUTANE
PENTANE
OVERALL
PHASE1
PHASE2
GAS
LIQUID1
fug. coeff. fug. coeff.
.86231
1.2403
.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
Output 177
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.
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.
water
methanol
ethanol
MEG
DEG
TEG
Glycol
Propylene glycol
dipropylene glycol
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
178 Output
H H ref H pg H res
Where:
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.
Output 179
Entropy definition
In Multiflash the entropy is calculated as
S S ref S pg S res
Where:
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.
180 Output
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.
The name of the active BIP bank for the problem e.g.
oilandgas4
Models
Phase descriptors
Problem
Pure Component
Databank
Results
Stream Types
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.
Output 181
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.
182 Output
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.
.
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
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
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
Keyword
Description
Unit
GOR
Gas-Oil ratio
scf/sbl
OFV
RB/sbl
OVIS
Oil viscosity
cPoise
ODEN
Oil density
lb/ft3
OCOM
Oil compressibility
1/psi
GFVF
ft3/scf
GVIS
Gas viscosity
cPoise
ZFAC
Gas Z factor
GDEN
Gas density
lb/ft3
CGR
bbl/MMscf
WVIS
Water viscosity
cPoise
WCOM
Water compressibility
1/psi
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.
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:
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.
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
Clicking on the Display button or double clicking on the topic allows you to
move to the related help text.
Help 193
About Multiflash
The About option provides information about the Multiflash software and your
license. It is particularly useful when reporting any problems to Infochems
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
Help 195
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.
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.
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 .
to carry out
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.
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 doubleclick 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
TCRIT
PCRIT
VCRIT
ACENTRICFACTOR
TBOIL
HFORMATION
SSTANDARD
114.231
569.32
2497000
2056.359
0.396
398.82
-208446.9
466.7252
g/mol
K
Pa
mol/m3
K
J/mol
J/mol/K
TMELT
HMELT
SMELT
CPMELT
VMELT
RUNIQUAC
QUNIQUAC
THLWATER
VHLWATER
DIPOLEMOMENT
POLARIZABILITY
QUADRUPOLEMOMENT
PARACHOR
RADGYR
HOCASS
GFORMATION
SFORMATION
TTRIPLE
PTRIPLE
HCOMBUSTION
V25
SOLUPAR
SOLIDSOLUPAR
ZCRIT
REFRACTINDEX
TFLASH
TAUTO
FLAMLOWER
FLAMUPPER
SPGRAVITY
EXPANSIVITY
OMARKS
OMBRKS
OMAPR
OMBPR
CNUMBER
REFVISCOSITY
REFVISST
REFVISPD
REFVISTW
REFVISLB
LJEVISC
LJBVISC
EOSC
TYPE
HDATUM
SDATUM
COMPREFNO
MCRKS1
MCRKS2
MCRKS3
MCPR1
MCPR2
MCPR3
HYDOC
HYD1
HYD2
HYD3
ASSBETA
ASDBETA
ASSEPSILON
ASDEPSILON
ASSGAMMA
ASDGAMMA
ASSDELTA
ASDDELTA
ASSFF
ASDFF
ASSAC
ASSBC
ASSKAPPA
SAFTKAPPA
SAFTEPSILON
SAFTGAMMA
SAFTFF
SAFTEK
216.37
20740.
50.00791
50814.48
5.8486
4.9360
0.
351.4
4.68040E-10
0.
16000.
-752.7986
216.38
2.1083
-5074150
6120.925
15447.5
0.2587676
1.39505
286.
479.
0.8
6.5
0.7066211
K
J/mol
J/mol/K
J/mol/K
mol/m3
K
m3/mol
debye
3
debye
(dyn cm-1) 1/4 cm3/mol
m
J/mol
J/mol/K
K
Pa
J/mol
mol/m3
(J/m3)1/2
(J/m3)1/2
K
K
vol %
vol %
1/K
Pas
Pas
Pas
Pas
Pas
J/K
m
1.
1.
1.
93.
J/mol
1/K
J m3/(mol)2
m3/mol
242.78
SAFTSIGMA
SAFTLAMBDA
SAFTM
SAFTQ
SAFTFRQ
VSRKS1
VSRKS2
VSRKS3
VSPR1
VSPR2
VSPR3
CPIDEAL
3.8373E-10
3.8176
m3/mol
m3/mol/K
m3 K/mol
m3/mol
m3/mol/K
m3 K/mol
-3721.3925
-1.3945
0.
1.9471999
20.
1.38007
568.95
.3775
0.
5407.5898
1.
-32384.514
76
290.
-5.7709999 0.
CPSOLID
5.
-24.
1.34E-5
2.094E-8
PSAT
3.
-7.9121099
-4.50132
260.
HVAP
1.
54909.031
0.
0.
LDENS
1.
2032.52
0.
568.381
LVISC
2.
-20.462999
1497.4
0.
0.
216.38
VVISC
1.
3.1191E-08
0.92925
0.
216.38
1000.
LTHCOND
5.
0.21867631
-0.00038267
0.
0.
216.38
VTHCOND
1.
-8758.
0.8448
0.
339.
1000.
STENSION
1.
0.05278999
1.2323
0.
0.
216.38
CPLIQUID
5.
224.83
-0.18663
0.
0.
216.38
SDENS
5.
8340.9004
-3.1515
0.
0.
133.15
VIRIALCOEFF 1.
.00027389999 -5.65219E-04
-1.161662E-05 2.58796E-06 284.38
DIELECTRIC
CARNUMBER
000111-65-9
FORMULA
C8H18
FAMILYCODE AA
UNIFAC
CH3
2
CH2
6
4.
5.6339999
10000.
-0.0085359998
216.37
-3.8043499
0.
568.381
0.375
1.3789999
398.83
55.092
2.1762921e-7
500
-2.71210E+10
0.
568.7
.00095890998
460.
0.
216.38
-3.63347E-04
1500.
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
THCOND
SURTEN
Pa
J/mol/K
J/mol
mol/m3
Pas
W/m/K
N/m
231.4
-47032
6255
0.0006945
0.1299
0.02341
275
427.8
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.
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.
Finally, click on OK in the message box and Close in the Model set dialogue
box.
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
Ethane
Propane
Butane
Hexane
Decane
0.45
0.20
0.10
0.10
0.10
0.05
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.
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,
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
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.
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.
0.45
0.20
0.10
0.10
0.10
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
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
The Lab Analysis form will then be displayed.
icon.
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. Weve started with the simplest case where we have
chosen to start the split at the heaviest SCN and only allocate one
pseudocomponent. Effectively we are only allocating physical properties to the
existing SCNs. Click on the Do Characterisation button and you will see a
message box such as
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 nparaffins) 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.
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.
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.
Example fluid:
Component
Amount (mol)
Methane
95
Ethane
Propane
Co2
0.1
N2
0.15
C6+
Pc (Pa)
Acentric factor
Molecular weight
863
1.5e6
0.9
250
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:
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
Chemistry Data Series
Vols I to XIV, Dechema
A good source of experimental data and BIPs is the series of volumes in the
Chemistry Data Series, published by Dechema. The UNIFAC model will
provide estimates of vapour-liquid and liquid-liquid equilibria without the need
for BIPs.
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.
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.
Enter BIPs, as given in the table below (in J/mol), using the Tools/BIPs option.
The bipset names are the model name followed by BIP, e.g. NRTLBIP3,
UNIQUACBIP2. BIPs are not required for UNIFAC as they are generated from
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
Wilson E
No BIPs
No BIPs
344.3
0.270
342.9
0.288
344.2
0.271
342.9
0.288
344.0
0.273
342.7
0.287
UNIFAC (VLE)
343.4
0.279
No BIPs
y1
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:
Flash at fixed P and T:
*** WARNING -20001 ***
Unstable solution, more phases exist.
T =298.25K P=1.00000E+05Pa ? CONVERGED ..UNSTABLE
Flash at fixed P and T:
*** 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 timeconsuming. 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
ngstrom units) and SAFTEK. In addition, the SAFTM parameter must be
specified. This is normally quoted as a ratio to the molecular weight, so it has to
be calculated for each polymer pseudocomponent knowing the molecular weight.
For polystyrene, for example, Gross and Sadowski give the ratio as 0.019, so for
a polystyrene pseudocomponent of molecular weight 100000, the SAFTM
parameter should be set to 1000000.019=1900, etc.
Our example polymer.mfl describes a simple binary of polystyrene plus butane.
The required properties of polystyrene are included in the input file, as are the
pure component SAFT parameters for butane. Load the input file in the normal
way and carry out a P,T flash at the input conditions supplied. The results show a
liquid-liquid split as expected.
You can also carry other flashes, such as a bubble point calculation
PC-SAFT has two interaction parameters. No interaction parameters for PCSAFT 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
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 25C (V25).
Estimated properties have been included in the file polymer3.mfl for polystyrene
and the predicted bubble point for the polystyrene-butane binary shown below.
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
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
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
P/bar
200
M= 96.4kg/mol
150
100
50
0
0
50
100
150
200
250
T/C
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.
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.
Hydrate model
The thermodynamic hydrate model consists of lattice parameters for the empty
hydrate and parameters for the interaction of gas molecules with water in the
hydrate. There are different parameter values for each hydrate structure, Hydrate
1, 2 and H. In addition the hydrate must be associated with a liquid phase model
that is used to obtain the properties of water. It is important that this is the same
model that is used for water as a fluid phase.
Nucleation model
This model can be used to predict the nucleation of any hydrate phases and
provides an estimate of the temperature or pressure at which hydrates can be
realistically expected to form. The nucleation model is based on the statistical
theory of nucleation in multicomponent systems.
With the Infochem/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.
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
METHANE
ETHANE
PROPANE
ISOBUTANE
BUTANE
PENTANE
Moles
85.93
6.75
3.13
0.71
0.88
0.57
CO2
N2
WATER
1.31
0.72
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.
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
r
e
s
s
u
r
e
H yd r a t e z o n e
H yd r a t e fo r m a t io n cu r ve
H yd r a t e
r is k
H yd r a t e fr ee
H yd r a t e d is s o cia t io n cu r ve
or the Fixed
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.
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:
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.
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.
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
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.
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.
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)
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.
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 F, the maximum difference was 55 F, whilst the average
difference was 24 F. It appears that the accuracy of WAT measurements has
improved in recent years, but it is still difficult to measure; it is realistic when
assessing results to assume that experimental error in WAT values may amount
to several degrees. 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.
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.
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.
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 dont 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
53C and using DSC was 40 C. The predicted WAT for the CPM default is
49.5C and for the suggested DSC default is 37.7C.
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 nparaffin will be lower than the N90 set. In this case the heaviest n-paraffin is n76+ 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 53C 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.
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 C, 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.
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:
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 npentane 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:
Reservoir temperature
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.
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 dont 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.
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.
2.
3.
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.
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:
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.
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
There are other data that may be missing and have an effect on the predictions.
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%.
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.
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.
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 C 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 C and 200 bar
and to a combination of reservoir temperature (54.4 C) and bubble point (54.4
C and 156.2 bar)
The 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
2
1.8
1.6
wt% asphaltene
1.4
1.2
1
0.8
Exptl
0.6
0.4
0.2
0
0
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
RAE
0.94176
0.96636
0.94999
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
wt% asphaltene
1.60
1.40
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.
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).
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.
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 nparaffins has the effect of stabilising the asphaltene slightly.
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.
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.
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.
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 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.
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
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
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.
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.
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.
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.
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.
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.
Defining models
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.
Many .mfl files are provided and will provide examples of how to set up a model
definition.
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
584 ***
model_identifiers
or
PD pd_id erase
The following table gives the valid options and settings:
command
parameter
description
notes
pd_id
phase_type
model_identifiers
1. fugacity (K-values)
2. volume/density (optional)
3. enthalpy/entropy
(optional)
4. viscosity (optional)
5. thermal conductivity
(optional)
6. surface tension (optional)
erase
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
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
Index
A
About Multiflash 194
Activity coefficient equations in Multiflash 37
Activity coefficient methods 37
Activity coefficient model for gas phase 9
Activity coefficient models 6
see Models 37
Activity coefficients 177
Activity model worksheets 294
Activity Models 179, 180
Adding a component 69
Adding a user-defined component 72
Adding water to the system 209
Adding, inserting, replacing and deleting components
69
Additional calculations 20
Advanced Equation of state options 31
Amount of inhibitor required to suppress hydrates
255
Appendix - Multiflash Commands 3
Applicability 36
Aqueous phase labelling 178
Asphaltene matching 270
Asphaltene precipitation 287
Asphaltene with gas injection 300
Asphaltenes 51, 267, 299
Case study 51, 267
Defining Asphaltene model 51
Model 43
ASTM D86 distillation 104
Azeotropes 235
B
Backup file 26
Basic characterisation properties 109
Benedict-Webb-Rubin-Starling (BWRS) equation of
state 34
Benedict-Webb-Rubin-Starling model 34
Binary interaction parameters 10, 53, 54, 55, 57, 58,
294
Displaying values 55
Supplementing and overwriting BIPs 58
Temperature dependence 54
C
Calculate 17
Calculating asphaltene precipitation conditions 272
Calculating mercury partitioning and dropout 304
Calculating the bubble point curve 206
Calculating the dew point curve 207
Calculating the water dew point line 209
Calculating wax appearance temperature (WAT) 261
Calculating wax precipitation 264
Calculation options 11
Calculation output 175
Calculations 2, 19
see Flash calculations 141
Calculations with inhibitors 252
Can hydrates form at given P and T ? 252
CAPE-OPEN 7
CAPE-OPEN Interface 188
Carbon Dioxide high-accuracy model 36
Carry out a the flash calculation 199
Carry out an isenthalpic flash 21
Carrying out the flash calculation 23
Case studies 3, 197, 205, 243
Asphaltenes 51, 267
Combined solids 287
Delump 225
Getting Started 13
Hydrate formation and inhibition 243
Phase equilibria 205
Polymers 237
Pure component data 197
PVT Analysis 214
Refrigerants 229
Wax 50, 260
Change the composition 20
Change the pressure 20
Changing units 170
Characterisation 99, 107
Check for Updates 193
Choice of Analysis method 276
Chung-Lee-Starling model 45
Chung-Lee-Starling thermal conductivity method 45
Clearing previous problems 21
Combined solids 287
Combined Solids Model 52
Index 317
Commands 3, 311
Appendix 311
Tools/Command option 311
Component cannot be found 86
Component list 91
Components 2, 63, 65, 66, 67, 68, 69, 70, 84, 197
Adding a component to a stream 69
Databanks 63
Deleting components from a stream 70
DIPPR 63
Displaying pure component data 197
Inserting a component in a stream 69
Maximum number in stream 65
Normal components 63
Properties of normal components 63
Replacing a component in a stream 70
Selecting by formula 68
Selecting by name 66
Selecting by scrolling through list 66
Selecting by substring 68
Selecting components 66
Synonyms of components 67
Troubleshooting 84
User defined 72
Compositions 14, 23, 137, 171
Amounts and fractions 138, 170, 171, 176
Specifying compositions 137
Conditions 14, 137, 139
Conditions section of main window 137
Specifying compositions 137
Specifying enthalpy 139
Specifying entropy 139
Specifying internal energy 139
Specifying pressure 138
Specifying temperature 138
Specifying volume 138
Troubleshooting 139
Consider all types of solution 167
Constants 73
Co-Polymers 239
Corresponding states (CSMA) model 35
CPA model CPA 10
CSMA
Reference fluids 35
CSMA model 9
Cubic plus association (CPA) model 32
Current settings
Display 181
Customising the phase envelope plot 155
D
Data Availability 277
Data input 237
Databank not found 84
Databank not licensed 85
Databanks 7, 10
DIPPR 63
INFODATA 63
Default units 169
318 Index
Defining a mixture 65
Defining a problem in Multiflash 18
Defining models 312
Defining petroleum fractions 109
Defining phase descriptors and key components 314
Defining the asphaltene model 268
Defining the components 21
Defining the hydrate models 243
Defining the mercury model 303
Defining the models 22
Defining the problem in Multiflash 197
Defining the wax model 260
Deleting components 70
Deleting petroleum fractions 112
Delump
Case study 225
Delumping tool 113
Delumping tool - Case study 225
Dew point 143
Differences between the PR Model in Multiflash and
Aspen Hysys 60
Diffusion coefficient 46
Diffusion coefficients 46
DIPPR 7, 63
Displaying status for current settings 181
Distillation curves 102
Distribution of mercury species 308
Document Organisation 2
Dortmund Modified UNIFAC method 38
Dortmund Modified UNIFAC model 38
E
Edit 15
Editing petroleum fraction data 112
Electrolyte model 81
Enter a composition for the stream 199
Entering BIPs 232
Entering petroleum fractions 110
Enthalpy
Specifying for isenthalpic flash 139
Enthalpy definition 178
Entropy
Specifying for isentropic flash 139
Entropy definition 180
Equation of state models 30
Equations of State Models 30
Equations of state provided in Multiflash 30
Errors 176, 181
Convergence 176
Messages 181
Troubleshooting 52, 60, 84, 139, 165, 171, 181
Errors and warning messages 181
Estimated n-paraffin distribution 108
Eutectics 236
Example for blending 130
Example with asphaltenic crudes 133
Example with waxy crudes 132
Examples
Case studies 50, 51, 197, 205, 243, 260, 267, 303
Getting Started 13
Excel interface 7, 202
Exiting Multiflash 27
F
File 14
Files
Loading problem setup files 18
OLGA PVT file 184
Output file 173, 174
PIPESIM PVT file 183
Problem setup (mfl) files 18, 25, 26
Prosper PVT file 187
Saving a problem setup file 25
Saving results in an output file 27
Fitting the vapour pressure curve 31
Fixed phase fraction flash 144
Fixed phase fraction flashes 144
Flash calculations 10, 139, 141
Bubble points 143
Definition of a flash calculation 141
Dew point 143
Fixed phase fraction flash 144
Isenthalpic flash 143
Isentropic flash 143
Isochoric flash 143
Isothermal (P,T) flash 142
List of available flash calculations 142
Retrograde flash calculations 147
Troubleshooting 165
Type of solution 147
Flashes available in Multiflash 142
Flory Huggins model 38
Flory-Huggins 38
Fluid amounts 129
Fluid file name 128
Fluid Identification 14
Fluid phase model 244
Font 174
Fonts 182
Frame Tab 152
Fugacity coefficients 177
Fuller method 46
Fuller model 46
G
Gas and liquid Enthalpy based on saturated liquid
heat capacity 180
Gas injection 282
Gas phase models for activity coefficient methods 38
GERG model 36
GERG-2008 36
GERG-2008 (Infochem extension) 36
Getting Started 2, 13, 205
Groups not available for UNIFAC model 52
H
Hayduk Minhas method 46
Hayduk-Minhas method 46
Help 191
HELP 3, 17
Help Topics 191
High accuracy reference eos for water-ammonia
binary system 6
How to change a model 48
How to Enter Multiflash Commands 311
How to exit the program 27
How to specify models in Multiflash 47
How to use the delumping utility 114
Huron-Vidal-Pedersen mixing rule 5
Hydrate
Inhibitor Calculator 79
Nucleation model 41, 49, 245
Hydrate calculations 159
Hydrate calculations with Multiflash 246
Hydrate dissociation pressure at a given temperature
254
Hydrate dissociation temperature at a given pressure
254
Hydrate formation and dissociation pressure at given
temperature 250
Hydrate formation and dissociation temperature at
given pressure 247
Hydrate formation temperature at given pressure 249
Hydrate inhibitors 79
Hydrate model 39, 244
Hydrate models 11
Hydrate phase boundary 251, 254
Hydrates 39, 48, 243, 255, 301
Case study 243
Hydrate inhibition case study 255
Hydrate inhibitor model 42
Hydrate model 39
Phase boundary 251
Hydrates in water sub-saturated systems 41
Hydrates, Waxes and Asphaltenes 289
I
IAPWS-95 35
Ice model 245
Ideal gas equation of state 30
Ideal solution model 37
Including a petroleum fraction 210
INFODATA 7, 10
Infochem fluids databank 63
Inhibition
Hydrate inhibition case study 255
Model for hydrate inhibition 42
Inhibitor calculator
alcohols/glycols 79
Inhibitor Calculator 6, 11, 79
Inhibitor modelling 42
Initial Values Tab 151
Input conditions
see Conditions 137
Index 319
Input Conditions 2
Input data 102, 267
Input files
Loading a problem setup file 18
Problem setup files 18, 25, 26
Saving a problem set up file 25
Input section 14
Inserting a component 69
Installation 3
Interface to other programs 141, 202, 235
Excel spreadsheet 141, 202, 235
Interfaces 7
Internal energy
specifying as a flash condition 139
Introduction 1, 5, 9, 29, 63, 89, 137, 141, 169, 173,
183, 191, 197, 205, 243, 260, 267, 287, 293,
303, 311
ISAPWS-95 35
Isenthalpic flashes 143
Isentropic flashes 143
Isochoric flashes 143
Isothermal (P,T) flash 142
J
Joule-Thompson coefficient 12
K
Key components 145, 314
L
LBC 5
LBC viscosity model 10
Lee-Kesler (LK) and Lee-Kesler-Plcker (LKP)
equations of state 34
Lee-Kesler-Plcker (LKP) model 34
Limit the number of phases 167
Linear Gradient Theory 46
Linear Gradient Theory model 46
Liquid dropout and Wax precipitation curve 11
Liquid dropout curve calculation 158
Liquid enthalpy based on saturated liquid heat
capacity 179
Liquid thermal conductivity mixing rule 45
Liquid viscosity mixing rule 45
Liquid-liquid equilibria 234
Loading a existing MFL file 26
Loading a model from a .mfl file 48
Loading a problem setup file 18
Loading an existing problem file 18
Loading files
Loading problem setup files 18
Log file 27, 173, 174
Saving the log file 27
Lohrentz-Bray-Clark model 44
Lohrenz-Bray-Clark method 44
320 Index
M
Macleod-Sugden 2-phase variant (MCSA). 46
Macleod-Sugden method (MCS). 46
Macleod-Sugden model 46
Manipulating the Output 177
Mass fraction flash 144
Match bubble point 297
Matching 116, 122, 123, 128
Asphaltene flocculation 281
Dew and bubble points 116, 122, 128
Liquid viscosity 125, 126
Wax Appearance Temperature 123
Matching Density/Volume 122
Matching dew and bubble points 116
Matching liquid viscosity 125
Matching to asphaltene deposition data 281
Matching using petroleum fraction properties 116
Matching vapour viscosity 126
Matching wax data/WAT 123
Maximum water content allowable before hydrate
dissociation 251
Menu options 14
Mercury 9
mfl files 18, 25, 26
Mixing rules 31
Liquid thermal conductivity 45
Liquid viscosity 45
Surface tension 46
Vapour thermal conductivity 46
Vapour viscosity 45
Model definition 129
Model is not available 52
Modelling a polar mixture 230
Modelling asphaltene flocculation 43
Modelling hydrate formation and inhibition 39
Modelling wax precipitation 42
Models 2, 5, 9, 22, 29, 37, 48, 53
Advanced equations of state 31
Asphaltenes 43
Benedict-Webb-Rubin-Starling (BWRS) 34
Binary interaction parameters (BIPs) 53
Chung-Lee-Starling 45
Corresponding states (CSMA) 35
COSTALD model 43
Cubic plus association (CPA) 32
Diffusion coefficients 46
Dortmund Modified UNIFAC 38
Flory Huggins 38
Fuller model 46
Gas phase models 38
GERG model 36
Hayduk Minhas method 46
Hydrate model 39
Hydrate nucleation model 41, 49, 245
IAPWS-95 35
Ideal gas 30
Ideal solution 37
Lee-Kesler-Plcker (LKP) 34
Linear Gradient Theory 46
Liquid density model 43
Lohrentz-Bray-Clark 44
Macleod-Sugden 46
Mixing rules 31
Model definitions 29
NRTL 37
Pedersen 44
Peneloux density correction 31
Peng Robinson (PR) 30
PSRK 32
Redlich-Kwong (RK) 31
Redlich-Kwong-Soave (RKS) 31
Regular Solution 38
Selecting model set 22
Selecting new model 48
Solid models 39
SuperTRAPP 45
Surface tension 46
Surface Tension 46
Transport property 44
Troubleshooting 52
Twu 44
UNIFAC 38
UNIQUAC 37
Viscosity 44
Wax 42
When to use activity methods 38
When to use BWRS 34
When to use CPA 32
When to use CSMA 36
When to use cubic equations of state 32
When to use equation of state methods 30
When to use LKP 34
When to use PSRK 32
When to use ZJ model 33
Wilson E 37
ZJ (Zudkevitch-Joffe) model 33
Models and input requirements 74
Models for solid phases 39, 48
Models tab 6
Molecular weight and specific gravity 95
Multiflash
Calculations 142
Case studies 197
Conditions 137
Exiting the program 27
Getting Started 13
Interfaces to other programs 183
Models 29
Output 173
Overview 1
Software system 1
Starting the program 13
Units 169
Multiflash Error Codes 193
Multiflash Excel Interface 12
Multiflash main window 13
Multiflash Main Window 13
Multiflash phase equilibrium algorithm 10
Multiflash Software System 1
N
New Features 5, 9
New Features and Changes in Version 4.2 2
New Features and Changes in Version 4.4 and 4.3 2
New high accuracy reference eos 6
New icon for Asphaltene precipitation curve 11
No information on the amount of asphaltene in the oil
278
No reservoir or precipitation conditions 280
No reservoir pressure 279
No resin - asphaltene ratio 279
Normal components 63
DIPPR 63
INFODATA 63
Properties of normal components 63
Notes 294
n-Paraffin distribution 105
NRTL equation 37
NRTL model 37
Nucleation 248
Nucleation model 41, 49, 245
O
Obtaining properties from the Pure Component Data
option 200
Oil and gas systems 205
OLGA 184
PVT file 184
OLGA hydrate file 186
OLGA tables 7, 12
OLGA wax file 186
On-line help 191, 194
Other calculations 24, 308
Other flash calculations 212
Other flash calculations with hydrates 251
Other properties 110
Other thermodynamic models 43
Output 3, 27, 173, 174
Enthalpy datum 178
Entropy datum 180
Level of physical property output 164
Phase Identification 178
Saving the output file 27
Troubleshooting 181
Writing the results to a file 173, 174
P
PC-SAFT equation of state 33
Pedersen Model 44
Peng-Robinson (PR) model 30
Peng-Robinson 1978 (PR78) equation of state 31
Peng-Robinson equation of state 30
Performance enhancements 6
Petroleum Fluid Blending 127
Index 321
322 Index
R
Redlich-Kwong (RK) and Redlich-Kwong-Soave
(RKS) equations 31
Redlich-Kwong (RK) model 31
Redlich-Kwong-Soave (RKS) model 31
Reference fluids 35
Refrigerant mixtures 229
Refrigerants
Case study 229
Regular Solution model 38
Regular Solution theory 38
Reid vapour pressure 11, 162
Reid Vapour Pressure 162
Replacing a component 70
Results 14, 19, 26, 27, 173
Level of physical property output 164
Printing the results 14, 26
Results window 173
Saving the results in a file 14, 27
Results window 14
Retrograde 147
Retrograde condensation 147
Retrograde dew point 147
Retrograde Dew Point 11
RKSA 10
RKSA-Info, CPA and PR 10
Running Multiflash 2
S
Salt calculator 81
Salt component 5
Salt inhibition 256
SARA Analysis 97
Saturation P at reservoir T 272
Saving a PVT Analysis 101
Saving files
UNFACFIT.xls 293
UNIFAC 294
UNIFAC method 38
UNIFAC model 38
UNIQUAC 37
UNIQUAC equation 37
Table 17
Tables 7, 12
Tabular output 141, 183
Excel interface 141
Index 323
Z
ZJ (Zudkevitch-Joffe) model 33
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
324 Index