Académique Documents
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Version 3.3
5 Decemberr 2003
Disclaimer
While every effort has been made to ensure that the information contained in this document is correct and that the
software and data to which it relates are free from errors, no guarantee is given or implied as to their correctness or
accuracy. Neither Infochem Computer Services Ltd nor any of its employees, contractors or agents shall be liable for
direct, indirect or consequential losses, damages, costs, expenses, claims or fee of any kind resulting from any
deficiency, defect or error in this document, the software or the data.
Contents
Overview 1
Introduction .................................................................................................................................. 1
Multiflash phase equilibrium utility.............................................................................. 1
Chemreact ...................................................................................................................... 2
Multiflash Software System......................................................................................................... 2
Documentation ............................................................................................................................. 2
Overview........................................................................................................................ 2
New Features and Changes in Version 3.3 ................................................................... 3
Running Multiflash........................................................................................................ 3
HELP.............................................................................................................................. 4
Case studies ................................................................................................................... 4
Appendix - Multiflash Commands................................................................................ 4
Installation .................................................................................................................................... 4
Simple Tutorial 11
Introduction ................................................................................................................................ 11
Starting Multiflash...................................................................................................................... 11
Defining a problem in Multiflash .............................................................................................. 12
Problem setup file........................................................................................................ 12
Loading an existing problem file ............................................................................................... 12
Loading a problem setup file....................................................................................... 13
The results.................................................................................................................... 13
Input 23
Introduction ................................................................................................................................ 23
Input files.................................................................................................................................... 23
Menu options.............................................................................................................................. 24
File ............................................................................................................................... 24
Edit ............................................................................................................................... 24
Select............................................................................................................................ 25
Tools ............................................................................................................................ 25
Calculate ...................................................................................................................... 25
Table ............................................................................................................................ 26
Help.............................................................................................................................. 26
Toolbar buttons .......................................................................................................................... 26
Dialogue boxes, text boxes, tab controls, drop-down tables and menus .................................. 26
Commands.................................................................................................................................. 27
Models 29
Introduction ................................................................................................................................ 29
What is a model? ........................................................................................................................ 29
What types of model are available?........................................................................................... 29
Equation of state method ............................................................................................. 30
When to use equation of state methods....................................................................... 30
Equations of state provided in Multiflash ................................................................... 30
Activity coefficient methods ....................................................................................... 34
Activity coefficient equations in Multiflash ............................................................... 35
Gas phase models for activity coefficient methods .................................................... 36
When to use activity coefficient models ..................................................................... 36
Models for solid phases ............................................................................................... 36
Other thermodynamic models ..................................................................................... 42
Transport property models .......................................................................................... 42
How to specify models in Multiflash......................................................................................... 44
How to load a model.................................................................................................... 44
What the model definition means................................................................................ 46
How to change a model ............................................................................................... 47
Loading hydrate models .............................................................................................. 47
The Freeze-out model.................................................................................................. 48
How to define a wax model......................................................................................... 49
How to define the asphaltene model ........................................................................... 50
Combined Solids Model .............................................................................................. 50
Troubleshooting - models .......................................................................................................... 51
Incorrect path ............................................................................................................... 51
Model is not licensed................................................................................................... 52
Groups not available for UNIFAC model................................................................... 52
Binary interaction parameters .................................................................................................... 53
Number of BIPs related to any model......................................................................... 53
Components 61
Introduction ................................................................................................................................ 61
Normal components..................................................................................................... 61
Condensed components ............................................................................................... 63
Petroleum fractions...................................................................................................... 63
Defining a mixture (stream) in Multiflash................................................................................. 64
Specifying the data source........................................................................................... 64
Selecting components.................................................................................................. 65
Adding, inserting, replacing and deleting components .............................................. 68
Viewing and editing pure component data. ................................................................ 69
User-defined components .......................................................................................................... 71
Stream types ............................................................................................................................... 76
Hydrate inhibitors....................................................................................................................... 79
Inhibitor calculator ...................................................................................................... 79
Salt calculator .............................................................................................................. 81
Troubleshooting - components .................................................................................................. 83
Databank not found ..................................................................................................... 83
Databank not licensed.................................................................................................. 84
Component cannot be found........................................................................................ 84
Too many components in the mixture......................................................................... 85
Petroleum fractions 87
Introduction ................................................................................................................................ 87
Defining petroleum fractions ..................................................................................................... 87
PVT Analysis ............................................................................................................................. 88
Analysis method .......................................................................................................... 89
Component list............................................................................................................. 89
Fluid composition ........................................................................................................ 92
Wax Content ................................................................................................................ 95
Water cut...................................................................................................................... 96
Total amount of fluid................................................................................................... 96
SARA Analysis............................................................................................................ 96
Characterisation ........................................................................................................... 96
Saving a PVT Analysis................................................................................................ 99
Troubleshooting PVT Analysis .............................................................................................. 99
Sensitivity to characterisation ..................................................................................... 99
Presence of water......................................................................................................... 99
Calculating petroleum fraction properties ................................................................................. 99
Editing petroleum fraction data................................................................................. 101
Matching using petroleum fraction properties......................................................................... 102
Matching dew and bubble points .............................................................................. 102
Matching wax appearance temperature..................................................................... 105
Matching liquid viscosity .......................................................................................... 106
Problems defining a petroleum fraction.................................................................... 108
Problems when matching .......................................................................................... 109
Units 135
Introduction .............................................................................................................................. 135
Working units ........................................................................................................................... 135
Default units ............................................................................................................................. 135
Changing units.......................................................................................................................... 135
Changing units interactively...................................................................................... 136
Changing units in a problem setup file ..................................................................... 136
Changing the default input and output units ............................................................. 137
Troubleshooting - units ............................................................................................................ 137
Output 139
Introduction .............................................................................................................................. 139
The results window. ................................................................................................................. 139
Font........................................................................................................................................... 140
Writing the results to a file....................................................................................................... 140
Printing the output.................................................................................................................... 141
Calculation output .................................................................................................................... 142
Output to Excel .......................................................................................................... 144
Phase envelope output.............................................................................................................. 144
Errors and warning messages................................................................................................... 144
Displaying status for current settings....................................................................................... 145
Troubleshooting - output.......................................................................................................... 146
The output does not include everything expected .................................................... 146
Phase labelling ........................................................................................................... 146
Phase envelope........................................................................................................... 146
Fonts........................................................................................................................... 146
Help 151
Introduction .............................................................................................................................. 151
User Guide................................................................................................................................ 151
On-line help.............................................................................................................................. 151
Website support........................................................................................................................ 154
Technical support ..................................................................................................................... 154
Index 253
Introduction
Multiflash is an advanced software package for performing complex equilibrium
calculations quickly and reliably. The main utility is a multiple phase
equilibrium algorithm that is interfaced to Infochems package of
thermodynamic models and a number of physical property data banks.
The program also contains Infochems Chemreact utility for performing
simultaneous phase and chemical equilibrium calculations.
Chemreact
Chemreact is a utility for performing simultaneous phase and chemical
equilibrium calculations. Currently Chemreact can handle equilibria involving
combinations of one gas phase, one liquid phase and any number of pure solids.
It is interfaced to the same package of thermodynamic models and physical
property data banks as the phase equilibrium utility.
As in the phase equilibrium utility, Chemreact incorporates a phase stability
analysis procedure to establish automatically which phases are present at
equilibrium.
Chemreact can calculate equilibria for the following specifications:
fixed pressure and temperature
dew point at fixed pressure
dew point at fixed temperature
bubble point at fixed pressure
bubble point at fixed temperature
When using Chemreact the user does not need to specify any reaction
mechanism but only list all the possible products and reactants.
Documentation
The supporting documentation is grouped into sections.
Overview
This section describes what the Multiflash software is used for, what it contains
and how it is made available.
Running Multiflash
Each section provides details on different aspects of the software.
Simple tutorial
This section is based on starting the program and running a simple example with
step by step instructions.
Input
This section provides an overview of the various ways you can enter data and
commands in Multiflash for Windows.
Models
This section describes the mixture models available in Multiflash and shows how
to define a model. How and when to use models is reviewed, together with the
availability and use of model interaction parameters.
Components
The type of components that are available from Multiflash are defined, together
with a description of the physical property databanks available. This section also
shows how to search for and select components, including how to define and edit
data for petroleum fractions.
Petroleum Fractions
How to carry out PVT characterisation and calculate petroleum fraction physical
properties.
Input Conditions
The necessary conditions for carrying out different types of calculations are
defined, together with how to enter and change these within the program.
Calculations
The final step in running Multiflash, the specification of the calculations which
can be carried out, and the circumstances where they might be most appropriate,
are outlined.
Units
This section defines the standard working units of the software, the range of
options available for input and output units and how to change them.
Output
This section reviews the different levels of output available, where output is
reported and how it may be saved.
Case studies
Additional examples of how to tackle typical problems using Multiflash are
provided.
A Contents list and an Index are also supplied to help you find your way
around the User Guide.
Installation
Information on how to install Multiflash software is provided in the the separate
"Installation Guide for Multiflash for Windows".
Introduction
There are several improvements and extensions in Multiflash 3.3. The major
development is the inclusion of new models, particulalry PC-SAFT. One of the
major applications of PC-SAFT is the calculation of phase equilibria for polymer
systems, thus extending the industrail fields Multiflash can serve.
Changes have been made to improve the robustness of calculations, partly due to
difficulties in solution for polymer containing systems. In some cases you may
find that calculated results are vary slightly from previous versions.
Models
Descriptions and references detailing the models are provided in our "Models
and Physical Property Guide"
PC-SAFT
PC-SAFT stands for the Perturbed Chain Statistical Associating Fluid Theory
and it incorporates current ideas of how to model accurately the detailed
thermodynamics of fluids within the framework an equation of state.
It is a development of the SAFT model that has been shown to give good results
for a wide range of polar and non-polar substances including polymers. The
model appears to be one of the most accurate and realistic equations of state
currently available for modelling polymer systems.
Regular Solution
Regular solution theory can be used for vapour-liquid calculations for mixtures
of non-polar or slightly polar components. The theory is applicable to systems
which exhibit negligible entropies and volumes of mixing. However, it has been
largely superseded by equations of state
Flory-Huggins
Flory-Huggins theory is able to describe systems which include some long chain
molecules. It has consequently applied to model polymer systems but it has been
largely superseded by other models such as PC-SAFT.
User Guide for Multiflash for Windows New Features and Changes in Version 3.3 7
Dortmund Modified UNIFAC
The Dortmund modified UNIFAC is a variant of UNIFAC that is better able to
represent the simultaneous vapour-liquid equilibria, liquid-liquid equilibria and
excess enthalpies of polar mixtures. Like original UNIFAC, however, it does not
allow for the presence of light gases in the mixture.
Diffusivity
Multiflash now returns effective diffusion coefficients for a liquid of defined
composition. Gas diffusion coefficients are calculated using Fuller's method,
liquid diffusion using the Hayduk-Minhas method.
BIPs
The INFOBIPS databank has been expanded to include interaction parameters
for Wilson E, UNIQUAC and NRTL for mixtures containing aldehydes, ethers
and ketones.
Fluid characterisation
Supplementary information
The PVT Anaysis forms have been revised to clarify the required input
information for molecular weight and specific gravity.
Plotting
Also new in Multiflash 3.3 is a display that shows the plot of the experimental
compositional data compared to the fitted distribution.
8 New Features and Changes in Version 3.3 User Guide for Multiflash for Windows
Matching
The Matching facilities for bubble and dew points and liquid viscosity also
include a display of the experimental and matched data. The numeric values for
the matched data are also automatically displayed in the results window.
Asphaltene
The procedure for generating the asphaltene model parameters from titration data
has now been automated and included in the Matching Asphaltene Phase facility.
Databanks
The Infodata and DIPPR databanks have been restructured. This may not be
apparent to the user but will allow future versions to store efficientlly new
properties required by the introduction of new models.
Properties
The pure component record has been extended to include the pure component
SAFT parameters required by the PC-SAFT model. Actual values have been
supplied for typical solvents, values for polymers have to be entered as part of
the user defined data.
The Dielectric constant has been added as a temperature dependent property.
Again supplied values are limited to water, methonal and glycols, but the user
can of course provide supplemental data if necessary.
Components
Six new components have been aded to Infodata. These are
SF6
and the amines
MDEA
MEA
DEA
TEA
Piperazine
Data for some other components have been revised.
User Guide for Multiflash for Windows New Features and Changes in Version 3.3 9
Phase envelope plotting
The tracing of the phase boundaries has been improved to handle the ever more
complex phase behaviour predictions.
The allocation of a different colour to each new phase line has been automated to
clarify the phase envelpe plots.
Units
A choice of units has been provided for Surface Tension, and a tab for this
property has been added to the Units definition menu. A new tab has also been
introduced for diffusion coefficients.
The deafult set of units is SI. For the convenience of user we have also
introduced a global unit change to "All metric" or "All British". These units set
are described in more detail in Changing units on page 135.
Tables
Multiflash can be used to provide tabluar input for other application packages.
Of the commercially available programs supported in this way PIPESIM and
OLGA remain but HTFS has been removed. The table requirement has been
superseded. The existing tabular output has ben upgraded.
Interfaces
The CAPE-OPEN interface has been upgraded to version 1.0. The
Matlab/Simulink interface is also upgraded with each new Multiflash release.
10 New Features and Changes in Version 3.3 User Guide for Multiflash for Windows
Simple Tutorial
Introduction
This section concentrates on how to run Multiflash using a simple problem as an
example. The assumption is that the user is already familiar with Windows
terms and techniques.
Starting Multiflash
You start Multiflash by clicking on the MFW32 shortcut.
or
The results
The results of any calculations are displayed in the results section of the main
Multiflash window and the last set of input conditions echoed in the input
conditions section of the window. You can scroll up and down to look at earlier
calculations.The input conditions section of the main window will now look like
this
You can scroll up to look at the earlier bubble point calculation at a pressure of
10e5Pa.
Additional calculations
You can pre-set all the calculations you wish to carry out for any one problem
within the problem setup file. However, it is probable that once you have seen
the results of one calculation you may wish to make other changes or perform
other calculations.
Any of the input conditions may be changed by entering new values to overwrite
or supplement those shown in the input section of the main window. Simply type
the value for the input condition in the appropriate text box, ensure that all
necessary input conditions are defined for the flash calculation you wish to carry
out and then click on the appropriate flash icon or select the required flash from
the menu options.
Compositions for a mixture may be altered by clicking on the composition
button and editing the right-hand column of the drop-down table where the
amounts of each component are defined.
To replace a component or to add new components see Adding, inserting,
replacing and deleting componentsSome simple changes are shown below:
butane
Compositions
1. Type the number of moles of each component, in this case 0.4 for
butane and 0.6 for pentane.
2. Close by clicking on roll-up button if you wish. The table can
remain down if you prefer.
Pressure
Type the pressure in Pa., in this case 10e5, in the Pressure text box.
Additional calculations
Any of the input conditions may be changed by entering new values to overwrite
or supplement those shown in the input section of the main window. Simply type
the value for the input condition in the appropriate text box, ensure that all
necessary input conditions are defined for the flash calculation you wish to carry
out and then click on the appropriate flash icon or select the required flash from
the menu options.
Compositions for a mixture may be altered by clicking on the composition
button and editing the right-hand column of the drop-down table where the
amounts of each component are defined.
To replace a component or to add new components see Adding, inserting,
replacing and deleting components.
Phase envelope
You can also plot the complete phase envelope by
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.
Introduction
This section concentrates on the methods of providing input information for
Multiflash, rather than the specification of that input information, which will be
discussed in the sections relating to the various types of information which must
be supplied.
The information you need to supply will include
Model specification
Data sources for pure component data
Compounds in the mixture.
Input conditions including composition
Calculation (flash) to be carried out
You may also wish to alter
Units
Level of property output
You can supply all of the input specification interactively, all of the input
specification in a problem setup file or use a mixture of both.
Input files
An input file may contain a full specification of the problem or define only part
of it.
We have usually referred to the former as problem setup files (extension .mfl)
and have supplied several to use as test examples or templates for producing
your own setup files. As a minimum they should define the model, data sources
for pure components and model interaction parameters (BIPs) and components
for your mixture. Usually they will also contain a composition and possibly the
flash calculation and the input conditions related to it.
We recommend that any setup file that contains the numerical values for any
input variables also defines the units for these to prevent any mismatch on
loading.
Typical of partial setup files are those which are supplied to define a model
(extension .mfc). These contain a specification of the model and a list of phase
descriptors, which give the possible phases that may be encountered in
calculations. The .mfc files we supply normally define up to four phases: one
Menu options
Multiflash for Windows includes a menu bar and several drop-down menus.
These allow you to control all aspects of running Multiflash for Windows,
grouped under the main menu headings of File, Edit, Select, Tools, Calculate,
Table and Help.
File
The File menu controls the loading, saving, clearing and printing of setup files
and the saving and printing of results.
Where you need to define further items, such as the directory and file to be
loaded, a dialogue box will be activated.
If the setup files you want have been used recently, you may find them listed. To
load a setup file from the list, move the pointer to the file and double click on it.
Edit
This controls the normal windows editing functions of Cut, Copy and Paste,
which can be used on text in the results window.
Tools
The Tools menu allows you to use commands to access all options that are
supported by Multiflash. This is most useful for options which have not yet
been allocated a button or specific menu item in Multiflash for Windows. The
Tools menu also allows you to view and edit the properties of any component in
the stream and any binary interaction parameters being used. The Inhibitor
calculator allows you to add water and inhibitors without defining them in the
pure component list. It also allows you to define the amount of the inhibitor in
the water phase in mass, mole or volume units and the calculator then determines
the amount of inhibitor to be added to the overall composition in the units
currently in use. The Salt Calculator is part of the Inhibitor Calculator dialog
box. The Matching function amends the properties of petroleum fractions in the
stream to reproduce user supplied liquid viscosity, wax appearance temperature
and dew or bubble points. For the asphaltene phase the matching function
modifies the asphaltene model parameters.
Calculate
The Calculate menu option controls the choice of standard flash options,
tolerance calculation, phase envelope and chemical equilibria. Sub-menus are
activated for Standard Flashes, Bubble and Dew Point Flashes and Chemical
Equilibria. Dialogue boxes are activated for Fixed Phase Fraction Flashes, (see
Fixed phase fraction flashes on page 118), tolerance calculation, (see
Tolerance calculations on page 122), and phase envelope, (see Phase
diagrams on page 124).
Help
The HELP menu enables you to get help on a variety of topics, see Help on
page 151.
Toolbar buttons
Some of the most common menu options have been allocated individual Toolbar
buttons.(located in the Tool bar section of the main window or in individual
dialogue boxes)
will provide more details of the chosen model, including the name
of the associated BIP set.
Introduction
This section defines what a model is in terms of the Multiflash nomenclature,
what models are available and when you might wish to use them, as well as the
practical means of specifying and using them in Multiflash. For information on
specifying models, see How to specify models in Multiflash on page 44.
Detailed model descriptions may be found in our separate "Models and Physical
Properties Guide".
What is a model?
Within the context of Multiflash, a model is a mathematical description of how
one or more thermodynamic or transport properties of a fluid or solid will
depend on pressure, temperature or composition.
fiv = fil
v l
where f i is the fugacity of component i in the vapour phase and f i is the
fugacity of component i in the liquid phase.
The models used in Multiflash to represent the fugacities from the phase
equilibrium relationship in terms of measurable state variables (temperature,
pressure, enthalpy, entropy, volume and internal energy) fall into two groups,
equation of state methods and activity coefficient methods. The basis of each of
these methods is described below.
With an equation of state method all thermal properties for any fluid phase can
be derived from the equation of state. With an activity coefficient method the
vapour phase properties are derived from an equation of state, whereas the liquid
properties are determined from the summation of the pure component properties
to which a mixing term or an excess term has been added.
Multiflash may also be used to calculate the phase equilibrium of systems
containing solid phases, either mixed or pure. These may occur either when a
Mixing Rules
For highly non-ideal systems it is often useful to be able to use a Gibbs energy
excess model(e.g. UNIQUAC or NRTL) as part of the mixing rule for the
equation of state. The possibilities are outlined in the separate "Models and
Physical Properties Guide".
Reference fluids
The current model implementation includes reference equations of state for the
following substances: argon, iso-butane, n-butane, CO, CO2 , ethane, ethylene,
fluorine, H2S, hydrogen, methane, nitrogen, octane, oxygen, n-pentane, propane,
water (IAPSW 95), xenon, helium, hexane, heptane, octane, ammonia, neon,
propylene, R123, R152a, R124, R125, R134a, R22, R32, R11, R113, R114,
R115, R116, R12, R13, R14, R23, and RC318. Hydrocarbons between pentane
and octane are modelled as combinations of these substances. The equations of
state are taken from various sources and do not all have the same quality or
range of applicability.
Applicability.
The model is very accurate for pure substances that are included in the above list
of reference substances. It is also applicable to near-ideal mixtures such as air
but for the best results it is necessary to fit values of the binary interaction
parameters to match experimental data. The model should not be used for non-
ideal mixtures such as water + CO2 etc.
f i l = xi f i *,l
The ideal solution assumes that all molecules in the liquid solution are identical
in size and are randomly distributed. This assumption is valid for mixtures made
up of molecules of similar size and type, but for mixtures of unlike molecules
you must expect varying degrees of non-ideality. The activity coefficient, i ,
represents the deviation of the mixture from ideality, as defined by the ideal
solution.
Wilson E equation
This model may be used for vapour-liquid equilibrium calculations but it is not
capable of predicting liquid-liquid immiscibility. Binary interaction parameters
are provided in our INFOBIPS bank for some component pairs. If no BIPs are
included for your particular mixture then to obtain accurate predictions you must
supply binary interaction parameters values in the correct units, which are Jmol-
1
.
Wilson A equation,
This model, which is a simplified form of the Wilson E model, may be used for
vapour-liquid equilibrium calculations but it is not capable of predicting liquid-
liquid immiscibility. To obtain accurate predictions you must supply binary
interaction parameters (BIP) values, which are dimensionless.
NRTL equation
The NRTL model may be used for vapour-liquid, liquid-liquid and vapour-
liquid-liquid calculations (the VLE option should be used for VLLE). Again if
BIP values are not provided in the BIP databank, INFOBIPS, they must be
supplied for accurate predictions. In cases where the user does not specify any
value for the third adjustable parameter, ij , it is automatically set to 0.3 if the
VLE version of NRTL is specified or to 0.2 if the LLE version is specified.
Note that ij = ji so only ij need be supplied.
UNIQUAC equation
The UNIQUAC model may be used for vapour-liquid, liquid-liquid and vapour-
liquid-liquid calculations. There are UNIQUAC VLE and LLE variants as for
the NRTL equation. Again BIP values must be supplied for accurate predictions
if they are not included in INFOBIPS. For VLLE the variant chosen should be
guided by the BIPs available.
Flory-Huggins
The Multiflash implementation of Flory-Huggins theory includes a regular
solution correction term. The Multiflash expression reduces to the standard
Flory-Huggins theory if all interactions parameters are set to unity. However, to
obtain reasonable results it is usually necessary to adjust the values of the
interaction parameters to fit the data.
UNIFAC method
The UNIFAC method is similar to UNIQUAC but the interaction parameters are
predicted based on the molecular group structure of the components in the
mixture. The is completely predictive and does not require the user to supply
BIPs.
Hydrate model
The original Infochem model uses a modification of the RKS equation of state
for the fluid phases plus the van der Waals and Platteeuw model for the hydrate
phases. An alternative model uses the CPA model for the fluid phases. The
hydrate models have also been extended to include hydrate structure H in
addition to structures I and II. The model can explicitly represent all the effects
of the presence of inhibitors, although parameters for the CPA model are only
provided for methanol, MEG and salt. CPA parameters for additional
thermodynamic inhibitors will be added in future versions.
The main features of the models are:
Our description of hydrate phase behaviour uses a
thermodynamically consistent set of models for all phases present
including hydrate structures I, II and H, ice, water, liquid and gas.
The vapour pressures of pure water and sublimation pressures of
ice are very accurately reproduced.
The following natural gas hydrate formers are included: methane,
ethane, propane, isobutane, butane, nitrogen, CO2 and H2S.
Other hydrate formers that are not usually present in natural gas but
which form structure I or II are also included. These compounds
are: SF6 , ethylene, propylene, cyclopropane, oxygen, argon,
krypton and xenon.
Parameters are provided for the following compounds that form
hydrate structure II in the presence of small help-gases such as
methane or nitrogen: cyclopentane, benzene and neopentane. These
compounds and the structure H formers listed below may be
present in condensate and oil systems.
Structure H hydrates form in the presence of small help-gases
such as methane or nitrogen but the formation temperatures are
significantly higher (about 10 K) than pure methane or nitrogen
hydrate. In practice it seems that structure II hydrates form before
structure H but if there is enough water structure H may be formed
too. The structure H model includes parameters for:
isopentane
Nucleation model
The nucleation model was developed in collaboration with BP as part of the
EUCHARIS joint venture. This model is an extension of the existing
thermodynamic model for hydrates described above. In order to extend the
nucleation model into the Multiflash program, the following enhancements to the
nucleation model were made:
The model was extended to cover the homogeneous nucleation of
ice and fitted to available ice nucleation data.
The model was generalised to cover in principle nucleation from
any liquid or gas phase.
A correction for heterogeneous nucleation was included that was
matched to available hydrate nucleation data.
An improved expression was adopted for fluid diffusion rates.
More robust numerical methods were introduced into the program.
The nucleation model provides an estimate of the temperature or pressure at
which hydrates can be realistically expected to form. The model is based on the
statistical theory of nucleation in multicomponent systems. Although there are
limitations and approximations involved in this approach it has the major benefit
that a practical nucleation model can be incorporated within the framework of a
traditional thermodynamic hydrate modelling package.
Many of the comparisons of model predictions with experimental data have been
made. In general measurements of hydrate nucleation result in an experimental
error of 2C and predictions are usually within this error band.
With the existing Infochem hydrate model and the nucleation model, the hydrate
formation and dissociation boundaries can be predicted between which is the
hydrate formation risk area.
Inhibitor modelling
Thermodynamic hydrate inhibitors decrease the temperature or increase the
pressure at which hydrates will form from a given gas mixture. The original
Infochem hydrate model includes parameters for the commonly used inhibitors:
methanol, salts, and the glycols MEG, DEG and TEG and for the less well-tested
inhibitors ethanol, iso-propanol, propylene glycol and glycerol. A new mixing
rule was developed for the SRK equation of state to model the effects of the
inhibitors on the fluid phases.
The hydrate model using CPA to model the fluid phases is limited in the current
version of Multiflash to hydrate calculations with pure water or with methanol,
MEG and salt. Additional parameters to extend the CPA model to cover the full
range of thermodynamic inhibitors listed above will be included in future
versions.
Salinity Model
Both salinity models operate at present on a sodium chloride equivalent basis.
The salt component model represents the effect of sodium chloride in aqueous
solution by a special equation of state component called salt component or
saltcomp. This model is designed to operate with the Advanced RKS equation
although it is also usable with the Advanced PR equation. The salt component
model cannot be used with the CPA model or any other equation of state.
The new electrolyte model is designed to be added on to any equation of state.
The models selection form allows it to be selected for use with the Advanced
RKS equation and the CPA model. It represents sodium chloride as a equimolar
combination of sodium and chloride ions. Future versions of Multiflash will
extend this to other ions.
Viscosity
Pedersen Model
This is a predictive corresponding states model originally developed for oil and
gas systems. It is based on accurate correlations for the viscosity and density of
the reference substance which is methane. The model is applicable to both gas
and liquid phases. The Infochem implementation of the Pedersen model includes
modifications to ensure that the viscosity of liquid water, methanol, ethanol,
MEG, DEG and TEG and aqueous solutions of these components or salt are
predicted reasonably well. We would recommend this method for oil and gas
applications. It is the default viscosity model for use with equations of state.
Reference: Pedersen, Fredenslund and Thomassen, Properties of Oils and
Natural Gases, Gulf Publishing Co., (1989).
Twu Model
This is a predictive modelsuitable for oils. It is based on a correlation of the API
nomograph for kinematic viscosity plus a mixing rule for blending oils. It is only
applicable to liquids.
Lohrenz-Bray-Clark method
This modelis a predictive model which relates gas and liquid densities to a fourth
degree polynomial in reduced density.
In Multiflash the fluid densities are derived from any chosen equation of state,
rather than the correlations proposed by Lohrentz et al. This has the advantage
that there is no discontinuity in the dense phase region when moving between
liquid-like and gas-like regions.
Multiflash also allows two variants of the LBC model. The first uses the original
LBC method to estimate the critical volume of petroleum fractions and takes the
critical volume of other components from the chosen data source. The second
variant fits the critical volume of each component to reproduce the liquid
viscosity at the boiling point.
The method is mainly applicable to the types of components found in oil and gas
processing but we would recommend that the Pedersen method is normally used
in these cases.
Thermal conductivity
Surface Tension
Macleod-Sugden method
This method predicts the surface tension of a liquid mixture based on the pure
component parachors stored in a databank. It is mainly applicable to the types of
component found in oil and gas processing.
Reference: Pedersen, Fredenslund and Thomassen, Properties of Oils and
Natural Gases, Gulf Publishing Co., (1989).
Diffusion coefficient
Fuller method
The Fuller method calculates gas diffusion coefficients. It is an empirical
modification of Chapman-Enskog theory.
Hayduk-Minhas method
The Hayduk-Minhas method calculates liquid diffusion coefficients. It consists
of a number of empirical correlations for different classes of mixture.
and finally, specification of a key component for each liquid phase so that it can
be identified when multiple liquid phases are found.
key Water 007732-18-5;
key Liquid1 not 007732-18-5;
key Liquid2 not 007732-18-5;
The CAS number is that for water. This format is general and unambiguous and
allows, for instance, for cases where the user has chosen the alternative H2O for
water. However, Multiflash will still recognise the original format of
Key Water water;
With the model successfully loaded you can continue to specify other aspects of
the problem such as the components and conditions.
For more information on commands see the Appendix to the printed User Guide.
Troubleshooting - models
We have tested the Multiflash software as far as is possible and corrected any
errors we have found, if you find any we havent please report them to us.
However, there is also a category of problems which we have run into ourselves
which can usually be resolved by the user. Some of those related to models are
discussed below, others will be outlined in the relevant section.
Incorrect path
All the problem setup files and model configuration files will be copied to the
installation directory. However, it is possible that you will wish to create a
working directory containing your own problem files, which is different from the
program installation directory. In this case you should copy the .mfc files into
your working directory or always refer to any .mfc files using the full path name.
For example, the sample file C4C5a.mfl contains the command
include pr.mfc
which should read in the contents of the pr.mfc file. If the pr.mfc file is not in
the same directory as C4C5a.mfl then you will see a message of the type
Click on Write to Output button, the output will be shown in the results
window:
show bipset RKSBIP;
BIPSET: RKSBIP
COMPS ORDER VALUES
1 2 0 .50558
The output includes the name of the BIP set. The Infochem convention is to use
the name of the model followed by BIP, e.g. RKSBIP, PRBIP, RKSABIP,
RKSABIP3 (for RKSA + Infochem mixing rule ), LKPBIP, WILSONBIP2,
NRTLBIP3, UNIQUACBIP2. If the BIP name is followed by a digit, this
indicates the number of BIPs for the model or no digit means that there is only
one BIP for the model. For the CPA model the bipset name is ASSOCBIP,
while the PC-SAFT BIPs are designated by SAFTBIP and SAFTBIP-2. Regualr
Solution and Flory Huggins BIPs are named REGULARBIP. If you define your
own problem setup file you can name the BIP set as you wish.
The components are referred to by the number they are assigned in Multiflash,
i.e. the order in which they were listed in the components list.
In this case the water methanol asymmetric parameters have also been fitted with
linear temperature dependence.
If you are using defined model sets or model configuration files then there will
only be one set of BIPs for any problem. If you define a model set using two
different models e.g. an equation of state in the vapour phase and an activity
model in the liquid phase you may have two BIP datasets, one for each model.
In this case highlight the BIP dataset of interest and click on Write to Output.
The BIPs for that model will appear in the results window.
In the grid of BIPs you will notice that the symmetric BIP is displayed twice.
You need only edit one of the cells, Multiflash will automatically enter this value
in the other cell once you click on OK.
You can save your new BIPs for the current case by saving the problem setup
file. If, for certain binary pairs, you wish to overwrite the Infochem supplied
BIPs every time you run Multiflash you may wish to store these in a separate
input file. You can create this file using the BIPset table or write the file with a
text editor using standard commands. You should refer to the Appendix -
Multiflash Commands on page 253. You should refer to the Appendix in the
printed User Guide for these. The default names for the model bipsets are the
model name followed by BIP e.g. WILSONBIP2 and the number of BIPs if the
number of BIPs is greater than 1.
A typical file of BIP data might be:
bipset PRBIP 1 constant butane pentane 0.01;
bipset PRBIP 1 constant pentane hexane 0.01;
bipset PRBIP 1 constant hexane heptane 0.01;
Alternatively you might wish to create a file containing BIPs for a single binary
pair but for various models. For example for our acetone water phase equilibria
case study, see Polar systems on page 179.
If your file of BIPs contains a range of binary pairs, some of which contain
components not in your current stream you will see a warning message for each
such pair:
*** WARNING -223 ***
One or more components in this BIP set are not
currently defined
but where the components are in the stream the new BIPs will be loaded and
included in any subsequent calculations.
You should note that if you change the model your input file of BIPs will be
overwritten by the standard OILANDGAS databank included in the model
definition and you will need to reload you BIP file.
If you wish to replace the current OILANDGAS databank with a previous
version, for instance to reproduce earlier results, this is done using the
Troubleshooting - BIPs
The methods of displaying and editing BIPs should limit the problems you are
likely to encounter. There remain two possibilities:
Units
Reference: We cannot stress often enough that to obtain correct results the BIPs entered
Dechema Chemistry Data must match the Multiflash definition and be in the correct units. A very good
Series (CDS) source of phase equilibrium data and BIPs is the Dechema Chemical Data Series
ISSN 0840-9645 which is in several volumes. It is useful to note that their standard convention is
Volume I to XVI to report activity model BIPs for VLE in cal/mole, which need to be converted
Publisher: Dechema to J/mol for use in Multiflash. The LLE BIPs for UNIQUAC and NRTL need to
be multiplied by the gas constant R (8.314 JK-1mol-1) for use in Multiflash.
Order of components
Equations of state with standard mixing rules usually have a single symmetric
BIP. However, activity coefficient models have two asymmetric BIPs. It is
important that you enter both asymmetric BIPs and in the correct cells so that
the binary pair is consistent with BIPs supplied.
If you do not use the Multiflash BIPset grid but use commands, either via an
input file or Tools/Command then the following problems may occur.
BIP databank
The name of the main BIP databank for equations of state is OILANDGAS and
this is the name included in all relevant model sets and .mfc files. However,
when you save a problem set-up the .mfl file will include the full name of the
BIP bank used at the time. For Multiflash versions 2.4 and 2.5 this is
OILANDGAS2, for version 2.6, 2.7 and 2.8 it is OILANDGAS3 and for 2.9,
3.0, 3.1, 3.2 and 3.3, OILANDGAS4. If you wish to update earlier input files
you can edit them using a text editor or change the BIP bank as described above,
Supplementing or overwriting BIPs on page 78.
For WilsonE, NRTL, UNIQUAC and refrig.mfc the default databanks are
INFOBIPS (VLE variants) or INFOLLBIPS (LLE variants).
Introduction
Multiflash recognises three types of component. Normal components are pure
compounds such as hydrocarbons, petrochemicals and chemicals which may
exist as gas, liquid or solid depending on conditions of temperature and pressure.
A petroleum fraction is a pseudocomponent, usually a complex mixture of
hydrocarbons, whose aggregate properties are characterised by standard tests, the
results of which may be found in PVT laboratory reports. Finally, a condensed
component is a pure solid phase, in Multiflash these are used in chemical
equilibrium calculations only.
The physical properties for each type of component are stored or defined
differently.
Normal components
The physical properties of normal components are usually stored in databanks.
Multiflash offers two, INFODATA and DIPPRTM. INFODATA is the Infochem
fluids databank which contains data on about 200 compounds and is always
supplied as part of Multiflash. DIPPR, produced under the auspices of AIChE,
currently has data for over 1600 compounds, but is extended annually. DIPPR is
offered as an optional module for Multiflash. For details of how to find a list of
components or to search for a specific compound see Selecting components on
page 65.
TYPE
CAS number
FORMULA
FAMILY code
Normal databank components will be TYPE 1, petroleum fractions will normally
be TYPE 12.
Condensed components
The INFOCOND databank includes about 140 solid compounds. The data are
limited to molecular weight, normal melting point, normal boiling point, the
enthalpy of formation in the condensed state at 298.15K, the standard entropy in
the condensed state at 298.15K and the heat capacity in the condensed state as a
function of temperature. It is intended for use with Infochem's chemical and
phase equilibrium module, Chemreact.
Petroleum fractions
Petroleum fractions are discussed in detail in Petroleum fractions on page 109.
To define a single petroleum fraction the program requires certain characteristic
properties and Multiflash will then estimate the other properties needed to
support the range of calculations available in the program.
The list of possible properties to support characterisation of the fraction are:
Carbon number
Molecular weight (g/mol)
Specific gravity at 60oF relative to water at 60oF
Normal boiling point
Critical temperature
Critical pressure
Pitzers acentric factor
However, not all of these are necessary. The minimum input sets are molecular
weight, molecular weight and specific gravity; molecular weight and boiling
point; boiling point and specific gravity; critical temperature, critical pressure
and acentric factor. Alternatively the boiling point can be used instead of the
acentric factor.
This input data can be supplied by the user for each fraction or provided on the
basis of a specified carbon number only. This is described in Defining
petroleum fractions on page 109.
The properties which are estimated, if they have not been provided, are:
Carbon number
Molecular weight
Normal boiling point
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.
The component will be transferred to the selected set by pressing the enter
key after the name or by clicking on the Add button.
If you are not certain whether a particular name in the databank list represents
the component of interest to you, or if are not sure that you have the correct
name for a component, you may wish to check the other names (synonyms)
stored in the bank for that compound.
Synonyms
To check the list of synonyms stored in a data source for any component type
the name in the Enter name text box, make sure the Synonyms option button is
selected and click on the Search button
You can also search the databanks using a partial formula. In the current version
of the program you may replace the number of any of the atoms in a component
by a *, but you must name all the different atoms in the compound you are
searching for. For example, C2Cl*H* will find all ethanes that contain chlorine.
Adding a component
Components are added to the selected list for a mixture as described earlier, by:
Double clicking on a component in a list.
By pressing the enter key after entering a name in the text box
(with Name option button selected).
Inserting a component
If you want to add a component to the selected list, but in a particular position,
perhaps so that the compounds are in order of carbon number in the program
output, then:
Select the compound as usual by entering the name or highlighting it in a list
Highlight (by clicking on it) the compound in the Multiflash list above which
you wish to insert the new component
Click on the insert button.
Deleting a component
If you wish to remove a component from the selected list then, in the
Compounds selected in Multiflash text box:
Select the component, then
Click on the Delete button
The compound will then be removed from the list.
Replacing a component
If you wish to replace one component with another you can do this without first
deleting it from the selected list.
Select the component to be replaced
Select the new component (either by typing in the name or using one of the
other selection methods)
Click on Replace.
The new component replaces the highlighted component.
Note that when you replace an existing component the amount
of the new component in the mixture remains the same as the
amount of the component it replaced unless you change the
composition in the Composition drop down table.
User-defined components
We do allow you to add user-defined pure component data, for instance when the
component you require is not available in our databanks. From the Data Source
select User-defined component from the drop-down list, then give the
component name in the text box and press Enter.
The physical properties for this component will be specified using the
Tools/Pure component Data option in Multiflash main window. Return to the
main window and activate this option, selecting your user-defined component
and the Edit option, choosing to edit Constants initially. The Pure component
data bank will appear with the Value column empty.
The equation types available for each property are set out in the Multiflash
Command Reference Manual, together with a description of each equation and
the number and order of the coefficients. All equations are specified as a
function of temperature in Kelvin and you should only enter coefficients which
have been fitted in Kelvin. Click on OK to define the property.
The minimum data required to perform any phase equilibrium calculation with
Multiflash using the basic equations of state are critical temperature, critical
pressure and acentric factor for each component. The data requirements are
model dependent and models other than the equations of state require additional
Stream types
For certain applications you may wish to define one or more sub-streams formed
from selected components of your overall input stream and describe these by
different models. Typically, this will be when you are using Multiflash to define
input data for a third party application such as a simulator where the composition
of the fluid will be changing with various unit operations. As the composition
changes different models may be more appropriate for different streams. A
simple example, shown in the Multiflash Excel manual, is to describe a mainly
hydrocarbon stream containing some water and glycol using a cubic equation of
state for high and low pressure separator flashes but to change to an activity
model to look at glycol regeneration from the recombined water streams.
We will describe how to set up stream types in Multiflash for Windows.
However, in the interactive version of Multiflash the composition of a sub-
stream cannot be changed without altering the composition of the overall stream
and it is difficult to define a realistic practical application for the interactive
version.
Initially we have defined an input stream containing 4 hydrocarbons, a
petroleum fraction, water and DEG and supplied a composition.
Once you have clicked on Define Model, a message box will confirm that the
model has been successfully defined. Click on OK to activate the Define Stream
Type text box. If you have not defined a Model Set prior to activating the Select
Stream Type option then you may wish to choose All components and call this
your overall stream type.
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.
You can then carry out any Multiflash calculations using that stream with its
selected components and the composition defined in the drop down Composition
table.
Hydrate inhibitors
Some of the pure components in INFODATA act as hydrate inhibitors, see
Inhibitor modelling on page 39. The most common are methanol, MEG,
DEG, TEG and salt. Any of these can be included in the component list as
described above and their composition defined as shown in Specifying
compositions on page 127. Indeed this is the way you should specify ethanol,
isopropanol, propylene glycol and glycerol. However, for methanol, glycols and
salt you can also use the Inhibitor Calculator.
Inhibitor calculator
The Inhibitor Calculator was included to make the addition of inhibitors easier.
The Inhibitor Calculator is designed to calculate the amount of inhibitor or
inhibitors to be added to the amount of water present in the stream to reach a
user defined inhibitor concentration. This concentration may be defined in mass,
mole or volume units.
Click Add button. Then the equivalent amount of inhibitor relevant to the
amount of water will be added automatically to the list of compositions of the
stream.
Click Close button to return to the main window.
Note that you can calculate the amounts of any combination of the four
inhibitors to be added to water but the total percent of the inhibitors must be less
than 100.
If you are carrying out fixed phase fraction flashes with glycol inhibitors at high
concentrations (of the order of 75 wt% plus) you should allow for the possibility
of the glycol forming a solid phase. The melting points of the pure glycols are
relatively high. To do this you should set up a freeze-out model for the glycol
Salt calculator
For the original salt model one of the components in the INFODATA databank
was called salt component. This is used to represent a salt pseudocomponent,
based on a sodium chloride equivalence, for use in calculating freezing point
depression or hydrate inhibition, see ( Calculations with inhibitors on page
197). For the new salt model, which is based on defining ions and not a salt
pseudocomponent, the ions Na+ and Cl- have been added to the databank. More
ions will be added in future versions.
To determine the inhibition effect of salt using either salt model you need to
provide a description of the salt content of the aqueous stream but often the data
for the salt, brine or formation/production water ion analysis will not be
available to you in the appropriate units. To help generate the data in the form
required by Multiflash we have an extended Tools/Inhibitor Calculator menu
option.
The water content of your stream can be defined from Select Components and
the Composition box or entered in the Water text box under the
Water/Alcohols/Glycols tab as described above.
Depending which salt model you wish to use you can either include the salt
component or the Na+ and Cl- ions in your component list by selecting from
INFODATA. However, an easier approach is to select either the Salt
Component Model or the Electrolyte Model tab from the Inhibitor Calculator.
With the appropriate tab selected you can define your salt from:
an Ion Analysis table
Clicking on the Add Salt button then initiates the calculation of either the
amount of salt component (Salt Component Model) or the amount of NaCl
(Electrolyte model) to be added to the stream in the units defining your
composition
You will also generate error messages if you define only negative or positive
ions in an Ion Analysis table
If you enter values on more than one analysis option the amount of salt to be
added will be taken from the table for which you activate the Add Salt button.
If you are carrying out fixed phase fraction flashes with a salt component present
in your stream and a low ratio of water to salt you should allow for the
possibility of a separate solid salt phase forming. To do this you should set up a
freeze-out model for the salt component using the Select/Freeze-out Components
option, see Solid freeze-out model on page 37.
The "Salt Component " option can only be used with the RKSA(Infochem"
hydrate model. If a salt component is present in the components list and you re-
define the model to CPA or RKSA(Infochem) + Elecrolyte options the salt
component will automatically be removed. Similarly, if the elecrolyte salt model
has been selected and Na+ and Cl- are present in the component list they will be
automatically removed on selection of the RKSA(Infochem) hydrate model.
If you wish to add both methanol and salt you enter the required concentrations
in the relevant Alcohols/Glycols and "Salt Component" or "Electrolyte" tab.
Clicking on Add in any tab will add the correct level of chosen inhibitor.
Troubleshooting - components
Despite all our efforts to test and debug the software there may be genuine errors
which should be reported to us. However, there are a range of problems,
commonly encountered, which can be rectified fairly easily. We hope the
associated warning messages are useful but if not please let us know.
TIP If the component you cannot find on the databank is present only in small or
trace amounts it may be possible to substitute a similar compound without
significant error. However, this will clearly depend on the particular calculation
and application.
TIP If you have some components of similar type and size in your mixture,
preferably present in small amounts, then it may be worth combining them to
reduce the overall number of components. This is particularly useful when
dealing with natural gases and gas condensates which have been analysed in
great detail.
Introduction
In the oil and gas industry a fluid may not be entirely composed of well defined
pure components. It may be composed of a combination of pure components
plus one or more pseudocomponents or petroleum fractions. Such fractions are
usually a complex mixture of hydrocarbons, whose aggregate properties are
characterised by standard tests, the results of which may be found in PVT
laboratory reports.
PVT Analysis
The PVT Lab Analysis form was designed to allow you to enter the information
supplied by PVT laboratories as quickly and easily as possible. As we actively
improve characterisation procedures the input form is modified, although the
basic structure remains the same. In Multiflash version 3.1 we provided two
forms in place of the single original. One form allowed you to enter a Single
total fluid composition, the other to mix separator gas and separator liquid
compositions.
In Multiflash 3.2 these forms were duplicated but with extended input to allow
the entry of a n-paraffin distribution. This was needed in 3.2 to support the new
Coutinho wax model. When a n-paraffin distribution is not available it can be
estimated for use with Coutinho's model and allowance is made on the Single
fluid and Liquid-Gas forms for the required input. In Multiflash version 3.3 a
fifth input form has been added for a Black Oil Analysis and the layout of the
common elements of all five forms has been modified.
Component list
A list of possible components is already provided based on a typical list from a
PVT laboratory. This consists partly of well-defined (discrete) compounds such
Only hydrocarbons can be added to the component list in the PVT Analysis. If
you try to add a component such as acetone then you will see a warning message
to indicate that the component cannot be added.
If you wish to add this component to carry out phase equilibria calculations then
you should characterise your fluid without the components present, return to the
main window and then add the component using Select Components.
If a proposed new component is already in the list and the amount of the
component is left blank, then the component will be ignored and the PVT
characterisation will proceed as normal. If the component is already in the list
with a either positive or zero amount then an error message will be generated
when you try to do the characterisation.
Only one datasource can be active when carrying out PVT characterisation. This
means that if the component you wish to add is only available in DIPPR (if you
have licensed this) changing the datasource from Infodata to DIPPR will also
change the source of pure component properties for all the discrete components.
If you wish the component list of your choice to be generated automatically you
can do this by adding the PVT Analysis component list to your MFCONFIG.dat
file. The easiest way to do this is to set up the list as you want it in Windows
and then use Tool\Show problem to reflect the changes in the main window.
Highlight the commands defining the pvtanalysis then copy and paste this to
your mfconfig.dat file. The next time you run Multiflash and use the PVT
Analysis the new component list will be generated automatically.
The GOR is a value provided by the PVT laboratory carrying out the analysis to
allow the user to recombine the gas and liquid analyses correctly in order to
obtain the correct fluid composition for the recombined fluid. We have altered
the description of GOR in the PVT form to reflect this. In Multiflash verion 3.3
the position of the GOR box has been moved. In order to carry out a
characterisation for the Gas and Liquid analysis you must have a composition in
both columns.
Compositions can be entered in either mass or mole % by using the drop down
menu at the top of the column and different units can be chosen for gas and
liquid. However, changing from mass % to mole % once amounts have been
entered will not lead to a unit conversion, the same values will be retained but in
different units.
As amounts are entered the Total % will be summed. If the Total % does not
equal 100% you will be offered the option to normalise the percentages before
the characterisation is carried out. Although the pseudocomponents will
normally run sequentially in terms of single carbon number it is possible to have
data from a non-laboratory source where the SCNs are not sequential. You can
still enter these, leaving gaps as appropriate; if the PVT is saved or recalled zero
amounts will be allocated for SCNs where no composition was provided.
In Multiflash version 3.3 it is now possible to paste fluid compositions into the
PVT Analysis form. For example, if you recive your report from the PVT
laboratory as an Exce spreadsheet, then provided your PVT Analysis compnent
list matches (or you have altered it to match) that from the laboratory, you can
simply copy the reported composition from the spreadsheet and paste it into the
appropriate column in the PVT Analysis form.
Our general advice is that if you have a lean gas, i.e. where the C6+ fraction is
only a minor proportion of the total fluid, you allow the program to estimate the
molecular weight of the heaviest SCN. For condensates and heavy oils it is
preferable to enter the molecular weight of the total fluid as this is an
experimental value. The molecular weight for the heaviest SCN shown in
analysis reports will probably have been assigned by the PVT laboratory using
generalised tables for petroleum fraction properties.
In order to give guidance when running Multiflash we have supplied some
warning messages. If the mole fraction of C6+ is <.05 and you supply a
molecular weight or specific gravity a warning message will be generated to ask
you if this is correct.
Conversely, if you have an oil where the mole fraction of C6+ is > .5 and you
fail to supply either molecular weight or specific gravity a similar warning
message will ask you to check this.
or
If the molecular weight appears to be too large this may well be correct, you
should just check the entry. If the molecular weight appears to be too small, it is
probably because the molecular weight of the heaviest SCN is less than that
allocated to the previous SCN in the distribution. This usually indicates a
mistaken entry, but this is not always the case and the program will continue
with the characterisation should you choose to ignore the warnings.
If you have a separate gas composition this should be entered in a similar way
before doing any characterisation but you must supply the GOR (gas to oil ratio)
on a volume to volume basis. Again there is a drop down menu for the choice of
units.
n-Paraffin distribution
A n-paraffin distribution can only be entered and used with the new
characterisation procedure, Infoanal2. It applies only to the C6+ fraction , but
data entry is similar to any other PVT phase composition
Wax Content
The ability to define the wax content was a new feature in the 3.2 PVT Lab
Analysis forms. The value corresponds to the values given by the UOP total wax
content test and is interpreted as giving the total C20+ n-paraffin content in the
stabilised oil.
It is a required input for the new Coutinho wax model where it is used to
calculate a n-paraffin distribution. If the wax content is unknown it too can be
estimated by ticking the box for Estimate Wax Content. If a n-paraffin
distribution is specified then the Wax Content and Estimate Wax Content boxes
are both disabled.
SARA Analysis
PVT Laboratories can often supply additional information on the fluid
composition in terms of a SARA analysis. This defines the relative amounts of
components which are saturates, aromatics, resins and asphaltenes. The amounts
of saturates and aromatics are used in some characterisation schemes. Our
current characterisation does not use this information but future extensions may
do so.
The SARA analysis is used by our asphaltene model. Currently, if you enter
amounts for resin or asphaltene these components will be added to your mixture
and will therefore affect your phase equilibria calculations. However, without an
asphaltene model you should not infer that you can calculate asphaltene
deposition.
In general the SARA Analysis should only be used with the asphaltene model. If
the amount of asphaltene or the resin/asphaltene ratio is unknown, it can be
estimated by the characterisation procedure by ticking the Estimate RA text box.
However, we recommend that you should use the experimental data if you know
them.
Characterisation
The characterisation procedure can be used to split or regroup the heavy end
from C6 to the heaviest SCN and to allocate physical properties to the resulting
pseudocomponents. From Multiflash 3.2 there are two characterisation
procedures, Infonanal1 (the original method) and Infoanal2 (the revised method
which also allows a n-paraffin distribution). If your problem has been stored in
an .mfl file then the choice of characterisation procedure will also have been
stored. Otherwise the first choice in the characterisation procedure is to choose
the characterisation method, by default this will be set to Infoanal2.
Perhaps the simplest case is to use the characterisation to allocate physical
properties to the SCNs already defined by the PVT Analysis. To do this, in the
Pseudocomponents section
Scroll Start pseudocomponents at until you reach the heaviest SCN in your
mixture
If you are using Infoanal1 then the pseudocomponents and their compositions
will be reflected in the main window . In this case the amounts should match
those entered. Thois will also be true for Infoanal2 but in this case we have
introduced an intermediate step which plots a comparison of the experimenta
analysis and the fitted distribution.
Sensitivity to characterisation
The distribution assumed in the original method is based on the Whitson Gamma
distribution function. Not all the PVT analyses we have tested are well
reproduced by this distribution and the revised method should provide a better
alternative. If you do see a warning that the default distribution parameter has
been used, then you should try the other distribution method or use the phase
envelope tracer to see how splitting and re-grouping pseudocomponents may
affect your phase calculations.
Presence of water
Defining a water cut using the PVT analysis form will alter the amount of water
in the overall stream but without changing the amounts of any components
which are not hydrocarbons and are not in the list of discrete components. It can
therefore affect the composition of an aqueous phase defined elsewhere in the
program.
and enter the values for one or more experimental dew points and the type of
dew point you are calculating (the Upper retrograde solution is the default
setting for dew point). Click on the Match button and the acentric factor of the
fractions will be adjusted until the calculated and experimental values match.
A plot will show a comparison of the experimental data fitted data
where C20+ is the 19th component. The adjusted acentric factor will be relected
in the pure component record
Prior to this a comparison plot will be generated for any any isotherm or isobar
for which experimental data was supplied. If only a single viscosity point is
matched the plot will be supplied for the isotherm.
The best advice we can offer is to make sure that you check that the units
(displayed next to each of the input text boxes) match the numerical values you
are putting in. A different section will discuss how to change units, see
Changing units on page 135.
Introduction
Once you have chosen the model for your mixture and selected the constituent
components, the next step is to specify the input conditions for the problem. In
Multiflash these are
Component compositions
Temperature
Pressure
Volume
Enthalpy
Entropy
Internal energy
The component compositions must be specified but only a subset of the other
conditions are needed depending on the calculation to be carried out. All input
conditions must be specified in the correct units. The units currently selected will
be defined adjacent to the relevant text box or drop down table. For information
on how to change the units see Changing units on page 135.
As you may wish to change the input conditions frequently, the majority are
grouped together in the Conditions section of the main window.
Specifying compositions
Component compositions can be specified or modified in three places.
Normally, they will be defined in the drop down table under Compositions.
However, it is possible to enter them under the PVT Lab. Fluid Analysis Form
(see PVT Analysis on page 110) or to enter the composition of an inhibitor
through the Inhibitor Calculator (see Inhibitor calculator on page 79).
Introduction
All the calculations carried out in Multiflash are flash calculations. This is true
even when you are only interested in obtaining the saturated liquid properties of
a pure component: the initial calculation in this case is finding the bubble or dew
point at a fixed temperature.
Multiflash is designed to carry out a series of single flash calculations except for
the phase envelope generator where a series of flashes are performed . Before
activating a calculation you must specify the components, compositions, model
and input conditions appropriate to the flash. After you have performed a
calculation you then make any changes you want to any input variable and
activate the flash again. When the phase envelope function is used to plot any
phase line the results of the individual flashes carried out are shown in the main
window. There is currently no other facility to generate automatically table style
output. Alternatively if you wish to generate tabular output frequently this can
be done easily using our Excel spreadsheet interface.
Of course, if you wish to calculate a series of flashes at changing conditions you
can set them up in a problem setup file. Once this is loaded all the flashes will
be calculated without further interaction on your part and you can scroll through
the output in the results window.
Alternatively click on the tool bar button, in place of the last three steps.
Isenthalpic flashes
These are flashes at fixed enthalpy. The most useful is the P,H flash which is
used when studying flow through valves or pipelines. A typical calculation is to
Determine the enthalpy of a stream at a given P,T (isothermal flash)
Enter the calculated enthalpy in the Conditions section
Drop the pressure by entering a lower pressure under Conditions
Click on the button or specify P,H flash from the menu bar.
The P,H flash also has a unique solution.
You can plot the phase boundaries for given constant enthalpy values.
Isentropic flashes
The isentropic, fixed entropy, flashes are used when you are looking at adiabatic
and reversible processes such as a turbo expander where you would use the P,S
flash. The H,S flash has applications in the turbine industry.
As with the isenthalpic flash, enter the value for the entropy which you want to
remain fixed in the Entropy text box, and enter the value for the other variable
(usually P or H). The P,S flash may be activated through either the tool bar
button or the menu, but the latter is the only option for activating the H,S flash.
You can plot the phase boundaries for given constant entropy values.
Phases
Multiflash is a multiphase phase equilibrium program that can handle up to nine
phases at any time with the current configuration. Any individual calculation
will consider the possibility of all specified phases but the maximum which may
exist together at equilibrium is limited to seven. The phase types that are
included in the current version of Multiflash are
Vapour
Liquid
Condensed (pure solid)
Hydrate
Wax
asphaltene
Phase names
The standard phase names are:
GAS vapour phase
LIQUID1 first liquid phase
LIQUID2 second liquid phase
WATER liquid phase with key component water
ICE solid phase with freeze-out model used for water
HYDRATE1 hydrate phase, structure I
HYDRATE2 hydrate phase, structure II
HYDRATEH hydrate phase, structure H
WAX wax phase
ASPHALTENE Asphaltene phase with key component asphaltene
If you apply the freeze-out model to any phase the default name is generated by
adding solid before the component name, e.g. SOLIDDECANE.
Using the command language you can of course allocate your own names to any
of the phases.
If you have created your own problem setup file you may have called these
phases by different names. In which case these names will appear in the
program in place of our standard nomenclature.
The phase names are used to identify the different phases when carrying out
fixed phase flashes and to identify the phases in the Multiflash output.
Key components
A key component helps to identify a particular phase. The rule used is that the
key component should be present in the phase to the maximum amount relative
to the total mixture composition. If the component name is preceded by the
keyword not , this means that the component should be present in the minimum
relative concentration.
The model sets and model configuration files supplied identify one liquid phase
as having water as the key component and the other two liquid phases in terms of
not being the water phase.
A key component is only needed when a flash calculation must identify a phase
uniquely (e.g. search for a particular phase fraction). Examples are the
fixedphase fraction flash or a phase envelope calculation.
If you request any of these calculations for a phase, the key component of which
is missing, an error message will be returned. For example if you try to calculate
a water dew point when there is no water in your stream the you will see the
following message:
For normal systems if you reduce the pressure along an isotherm from the
liquid or dense gas region you reach its bubble point, where the gaseous
components no longer remain dissolved in the heavier liquid components and
separate off as a gas.
Tolerance calculations
Tolerance calculations are used to determine the amount of a component or
mixture that must be added to the original stream to achieve a given phase split.
A typical application is to determine how much inhibitor is required to suppress
hydrate formation. Another example might be to determine the amount of water
needed to saturate a gas. Tolerance calculations are carried out at fixed
temperature and pressure and for a fixedphase fraction specified in moles.
To carry out a tolerance calculation specify the model and the components in
your stream. These should include the component or components for which you
wish to determine the amount to be added. In the Composition table specify the
composition for your mixture. The component/components for which the
tolerance calculation is being carried out need not be there in zero amount if they
are already present in the stream. However, it is more usual to set their
composition to zero, for example zero amount of methanol when you wish to
calculate the amount needed to inhibit hydrate formation. Using
Calculate/Tolerance Calculation open the subsidiary window
Phase diagrams
A major addition to Multiflash was the ability to calculate and plot phase
envelopes. It is possible to trace any phase boundary including gas, liquid and
solid on pressure-temperature co-ordinates. A V/L Autoplot function traces the
primary dew and bubble point curves. You should note that the phase envelope
should only be used for models based on an equation of state (or at low pressures
for activity models).
In version 2.9 we added the ability to trace selected phase boundaries on the
basis of mass or volume fraction in addition to mole fraction and the nucleation
boundary. In 3.0 we increased the flexibility of the phase boundary tracer to
include the plotting of constant enthalpy, entropy, volume or free energy
boundaries. In 3.1 we improved the boundary tracer to handle cases where the
line crosses a phase boundary at which there are no degrees of freedom
according to the phase rule. The common example is the vapour-liquid
saturation line for a single component. In version 3.2 we have generalised the
plotting facility so that for any chosen phase boundary it is possible to plot any
phase or property against another. The 3,3 release of the phase envelope has not
made any technical changes to phase boundary calculation but includes a useful
improvement which automatically changes the colour of any new boundary.
The Phase envelope is activated through the Calculate/Phase Envelope menu or
using the phase envelope button, .
The resulting window has three sections. The first
If you choose to plot any of these then you will be reminded of the current unit
setting for the property when you enter the value.
The final section allows you to set P,T boundaries for the calculation and to set
the properties you wish to see displayed on the x and y axis. For normal phase
envelopes these will be temperature and pressure.
A typical example might be a VLE plot for a hydrocarbon fluid with gas present
in zero mole fraction. The axes will be pressure versus temperature.
Before the new plot is displayed you will be reminded that you have altered at
least one of the axis properties and that boundaries plotted on the previous axes
will be lost.
If you wish to return to the standard P,T axes to plot you must remember to alter
the axes yourself in the Frame tab, they will not be reset automatically.
The Frame tab allows you to change the maximum number of points calculated
at any one time. The default is 100. If, when plotting any phase boundary it is
possible to calculate more points, then a displayed message will allow the phase
envelope calculator to continue or to stop at any point.
Similarly, the individual flash results which appear in the first three columns in
the window are marked with C or D so that the numeric values at these point can
be determined.
Phase envelope output:
T/K P/bar
71 380.475 97.055
72 378.655 99.477
73C 377.068 101.23
74 375.109 103.10
75 371.322 105.97
Write to Excel
Although you can call all Multiflash functions directly from an Excel
spreadsheet, including the Phase envelope function, you can also transfer the plot
and phase boundary points to Excel. Once you are happy with a plot clicking on
Write to Excel will generate a spreadsheet with a Chart corresponding to the
tabular values reflected in the main window with the values themselves posted to
a worksheet.
The Write to Excel facility is supported for Excel 97, 2000 and XP but not for
Excel95.
Activity coefficients may not be a valid property for all components in all
phases. This will depend on the component and the model. If the property is not
valid N/A will be displayed.
The default setting is equivalent to the first two options being selected. To
reduce the output click on OK with all options deselected. Otherwise select the
properties for which you want output. If you choose Heat Capacity and Speed of
Sound the phase amounts and composition plus the volume and thermal property
output are also automatically selected. Note that the thermal properties relative
to elements option is not available without the first two options being selected.
Examples of the property output options are shown in Calculation output on
page 158.
If you are doing chemical equilibrium calculations you may wish to see the
values of thermal properties (enthalpy, entropy, internal energy and Gibbs
energy) relative to elements in their standard states.
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:
Chemical reaction
Multiflash has a chemical equilibrium module which allows the simultaneous
calculation of phase and chemical equilibrium. The phase equilibrium is
currently limited to equilibria involving combinations of one gas phase, one
liquid phase and any number of pure solid phases. The flash options available
are
P,T Chemical Equilibrium
Dew Point Chemical Equilibrium
Introduction
A significant proportion of the apparent errors and problems reported for
Multiflash can be tracked down to a mismatch between the units the user thinks
he/she is using and those currently set in the software. The importance of
matching units cannot be stressed too much. Having said that, what units are
available for you to select?
Internally all Multiflash calculations are carried out in SI units. This cannot be
changed. The default input and output units are also SI. Unless you change the
units any numerical input values for any property will be assumed to be in SI.
The input amounts for any calculation are total amounts. The output defaults are
that individual compositions of any phase are given as fractions but the amount
of the phase is the total amount.
Working units
Internally all Multiflash calculations are carried out in SI units. This cannot be
changed.
Default units
The default input and output units are also SI. Unless you change the units any
numerical input values for any property will be assumed to be in SI.
The input amounts for any calculation are total amounts. They may be set as
percentages in the PVT Analysis Form or the Inhibitor Calculator, but they will
be converted to absolute amounts for calculation or display in the Composition
drop down table. The output defaults are that individual compositions of any
phase are given as fractions but the amount of the phase is the total amount.
Changing units
You may change any of the input or output units. In Multiflash 3.3 units can be
altered as a "block" by choosing "All Metric" or "All British". Units for all
properties will be reset to:
All Metric;
mole, DegC, bar,m3/mol, J/mol, J/mol/K, cP, W/m/K, N/m, m2/2
To view the currently selected units for any property click on the corresponding
tab. To change the input units for any property click on the option button next to
your choice of unit in the Input unit column. This button will then be set. Do
the same in the Output unit column to change the output units for that property.
The input and output units do not have to match.
The output composition may be changed from fractions to total amounts on the
Amounts tab. It is not possible to change the input composition to fractions.
This Tab control panel for units selection can be also accessed by clicking the
Units button from a dialog box such as Phase envelope, Tolerance calculation,
defining Petroleum fractions , Pure Component Data, Match Dew Point, Match
Bubble Point and Tables.
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.
Introduction
The output from Multiflash appears in the results window which occupies the
bulk of the main window. The output is also written automatically to a log file,
called MFLASH.LOG. It is also possible to print results or to write them to
another file of your choice. How you do this will be discussed in Writing the
results to a file on page 156.
Font
The default font for displaying results in the output window is Lucida Console,
10 pt. This can be changed by the user from the Tools/(Output Window)
menu option.
The possible fonts available will depend on the particualr PC installation. When
changing fonts we recommend that you always choose a mono-spaced font so
that the column output is retained.
If you have previously highlighted a section of the output then the message box
offers the option of writing the selected text to file.
A dialogue box allows you to choose the file name and directory. The
convention is that the extension for output files is .out, but you may alter this if
you wish.
Calculation output
Calculation output will vary slightly depending on the type of calculation and the
level of physical property output specified but will be in the style
The first line of output reports the temperature and pressure. These may be either
the input conditions or the values calculated from the flash.
This is followed by three messages:
No. Phases reports the number of phases that have been found at the particular
temperature and pressure.
CONVERGED means that the calculation has been completed successfully. If a
solution has not been found then error messages would be produced and any
results would be labelled FAILED. If a warning has been generated then you
may see the message ?UNCONVERGED. In the latter two cases the error or
warning messages should be read carefully to assess the problem.
Multiflash can only check for STABLE means that no further phases (out of the list provided) will form.
the stability of a solution with Sometimes a solution may be labelled as UNSTABLE, meaning that further
respect to the formation of phases would form if more phases were allowed for in the problem setup. An
another phase of a type example might be if only vapour and one liquid phase are specified but in fact
already specified. For the true solution is vapour-liquid-liquid. If you want to look for the extra phase
example, if you have only then you must include an additional phase descriptor in your model definition.
defined two liquid phases the If, however, you are at very low temperatures you may be looking at a
possible formation of a metastable solution and wish to retain only the number of phase descriptors
vapour cannot be checked already defined. The results of a hydrate nucleation calculation will always be
labelled unstable. It is also possible to see the message MARGINALLY
STABLE. This means that, although the solution is stable, changing the
conditions slightly might result in the formation or disappearance of a phase, for
example near the critical point.
The remaining output depends on the setting for the physical property output
level. For each phase the phase name is given underneath to identify it uniquely.
The previous example shows output from the default setting.
The column labelled OVERALL gives the total mixture properties (where
applicable). The default composition units are moles. The compositions shown
are actually mole fractions, but the Phase totals are in moles. If mass-based
output units for amounts are chosen the compositions displayed are mass
Activity coefficients may not be a valid property for all components in all
phases. This will depend on the component and the model. If the property is not
valid N/A will be displayed.
Finally, values for diffusion coefficients are displayed. If the model definition
has been set to include diffusivity then the output will automatically include
diffusion coefficients. If Diffusivity has been set for property output but not
included in the Model Set definition then the property label will appear but not
the numeroc values.
PHASE1
GAS
Diffusion coefficient (m2/s )
ACETONE WATER
ACETONE 8.00080E-06 1.86663E-05
WATER 1.86663E-05 4.29283E-05
PHASE2
LIQUID1
Diffusion coefficient (m2/s )
ACETONE WATER
ACETONE 7.15035E-09 2.96215E-09
WATER 2.96215E-09 4.55884E-09
A full list of the Multiflash error codes is now available through the HELP
function.
Warning messages should be checked carefully. In many cases they may be
ignored if the cause is understood.
Errors are usually associated with Multiflash output indicating a failure to find a
solution or that the results may be invalid.
Show options
Amounts Displays the amount of each component in the stream
BIP databank The name of the active BIP bank for the problem e.g.
oilandgas4
Black Oil Analysis Details of the input to the Black Oil Analysis PVT
form
Characterisation The correlations used to predict physical properties of
method the petroleum fractions e.g. INFOCHAR
TBSOEREIDE
Components List of components in the input stream
Models List of the model set
Phase descriptors Phase descriptor names for the phases to be included
in calculation
Problem Full definition of the current problem
Pure Component The pure component databank current at the time of
Databank request
PVT Analysis Description of the settings in the PVT Lab Analysis
form
Results Repetition of the results from the last calculation
Stream Types Displays number and names of active streams
For brevity much of the output from the show option will be in keyword form.
For instance, under Characterisation method, TBSOEREIDE is the name of the
correlation used for calculating the boiling point of a petroleum fraction. The
alternative would be TBAPI.
The output for Show Models will depend on whether the model has been set
interactively or loaded in as part of a problem file. In the latter case the
thermodynamic model may only be referred to as MEOS. To obtain more
information you would still have to use the Tools/Command option and type in
Show model meos;
If the model has been defined interactively more detail is given at the initial
Show Models stage e.g. MPR is the Peng-Robinson model.
Phase labelling
The phase names attached to each of the possible phases which may form
enables you to keep track of the phase output. One case where some confusion
may arise is for dense phases, where it is not possible to decide unambiguously
whether the dense fluid is a liquid or a gas. In this case the phase name may
change with slight alterations in conditions. This does not affect the correctness
of the results or phase properties, it is only the label attached to the phase that is
ambiguous.
Phase envelope
This facility is unusual in its ability to plot multiple phase lines. The phase
envelope output is designed so that you can build up complex phase diagrams by
adding different phase boundaries. If you forget to clear the plot or clear the
problem setup this may lead to the plot from a new problem being superimposed
on that from an earlier plot. In this case either Delete the individual phase
boundaries from the earlier plot using the Options facility or Clear the whole plot
and start again.
Fonts
Occasionally users have reported not being able to read the output in the results
window. This appears to be the result of particular PC installations where the
font type or size has been re-set to choices that are incompatible with our
display. They can be set to acceptable choices, see Font on page 140.
Introduction
In addition to using Multiflash to do stand-alone calculations it is possible to
create property data files for use by other application programs. Multiflash can
currently produce Pipesim PVT files and files for input to OLGA. The faciltiy to
produce HTFS Process Simulator Interface Files (PSF) has been removed from
Multiflash 3.3.
User Guide for Multiflash for Windows Interfaces with other programs 147
Click on Calculate table
Assuming there are no problems the output will go directly to the .PVT file, it
will not be sent to the results window. In the results window you will see the
message
Pipesim table generation:
table pipesim "Pipe6.pvt" pressures 1e5 5e5 10e5;
temperatures 350 400 450;
title "Output for pipe 6";
*** Generating Pipesim table - please wait ***
*** Table successfully generated ***
If any of the input is unacceptable, such as specifying negative pressures or
absolute temperatures or if Multiflash cannot solve the flash calculation at any
grid point then a warning message will appear
.
It should be noted that any user BIPs specified by the user in Multiflash will not
be carried forward to the .pvt file. However, in line with recent changes to
PIPESIM .pvt files written with Multiflash will contain information on the
version of OILANDGAS and the viscosity model used.
OLGA
OLGA is a general purpose transient simulator for modelling fluid flow in
flowlines and pipeline systems. It is a product licensed by Scandpower A/S.
148 Interfaces with other programs User Guide for Multiflash for Windows
Multiflash can produce a PVT data file for use by OLGA. The file contains all
the physical property information required by OLGA. It consists of a series of
flash calculations on a grid of pressure and temperature values. The information
stored includes all the properties required by OLGA for either two-phase or
three-phase problems as set out in Scandpower Technical Note No. 1.
To generate the file:
Define the models (which must include models for surface tension, thermal
conductivity and viscosity) and the mixture (components and composition) as
usual
Select Table in the menu bar, then
Select OLGA
Fill in the subsequent dialogue box. with the pressure and temperature
grid points and the name of the output file. The recognised suffix for
OLGA tables is .tab. This will be allocated automatically if you use the
Browse facilty to identify a suitable directory and save the file from
there. Alternatively you can typ in the .tab suffix as aprt of the file
name. If you want the file saved in a particular directory you must
enter the full pathname, otherwise the file will be saved in the current
default directory. OLGA requires a File id (strating with a letter not a
number). If you don't provide one Multiflash will assign one
automatically.
User Guide for Multiflash for Windows Interfaces with other programs 149
.
CAPE-OPEN Interface
Infochem has been an active participant in developing and testing the CO
standards. The Multiflash CO modules implement version 1.0 of the standard
and support the ThermoSystem and Property Package interfaces. The interface
has been tested for interoperability with Aspen+, gPROMS and HYSYS.
To generate a file from Multiflash that can be read by the Multiflash CAPE-
OPEN module simple set up the problem in Windows as usual. Instead of
saving the Problem Set-up you use the file option for Export CO Property
Package. A separate manual for the CAPE-OPEN Interface is provided on the
Multiflash CD-ROM.
150 Interfaces with other programs User Guide for Multiflash for Windows
Help
Introduction
Help is provided in various ways:
The printed User Guide
On-line Help
Website support
Technical support
User Guide
The User Guide explains how to use Multiflash in detail and contains several
case studies and a simple tutorial, plus an Appendix listing useful commands
which can be used through Tools/Command in the menu.
On-line help
The on-line help will be familiar to regular users of Windows applications. It is
accessed through the HELP menu
Related topics are further sub-headings and more help is displayed by selecting
any of these.
Some of the help text may be displayed in green. If this is underlined with a
solid line, clicking on the text will allow you to jump to another help screen
related to the text. If the text is underlined with a dotted line, clicking on it will
result in a pop-up box containing a glossary definition or a margin note.
Selecting Search, either from the HELP menu or via the Search button in the
on-line help window allows you to specify a particular topic you are interested
in, either by typing in a description or selecting from the list displayed.
Website support
We now have an additional level of help. Our website, http://infochemuk.com
can now be used to report bugs found in Multiflash and to see any
bugs/problems we or other users have found. Where these have been fixed we
will tell you which release version does or will contain the corrections. If we are
still considering how to tackle the problem but know of a work around we will
advise you of our suggestions. We also hope in the near future to allow you to
download updates from our website to pick up changes to the software. At the
moment this is limited to the front-end and all the relevant drivers for the
dongles.
Technical support
If you need further assistance contact us at:
Infochem Computer Services Ltd.
13 Swan Court
9 Tanner Street
London SE1 3LE
UK
Telephone: +44 (0)20 7357 0800
Fax:+44 (0)20 7407 3927
e-mail: support@infochemuk.com
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.
User Guide for Multiflash for Windows Case studies - Pure component data 155
Selecting Ideal Mixing from the Activity Model selection. Choose the gas
phase model as Perfect gas. The recommended and default model for transport
properties is Mixing rules
You will see a message to say that the Ideal Mixing model set has been
successfully defined.
Click on OK
For more information on models see Models on page 39.
Specify the pure component of interest in this case octane
156 Case studies - Pure component data User Guide for Multiflash for Windows
or
Selecting the formula option button, typing C8H18 in the text box,
clicking on Search, selecting octane in the Components in databank text
box, then clicking on Add or double clicking on octane
Specifying the physical property output level.
If you are interested in pure component data you will probably want to output all
available physical property data except thermal property data relative to
elements.
Select Select in the menu bar and then select Property output.
In the resulting dialogue box, the first two are the default options for output of
thermodynamic data, click Heat capacity/Speed of Sound and the set of
transport property data and finally click on OK.
User Guide for Multiflash for Windows Case studies - Pure component data 157
In this case where we have a pure component the composition is not important
provided it is a positive value.
In the main window, click on composition, then type 1.0 in the right-hand
column of the table next to octane.
To obtain the properties of liquid octane on the saturation line you must carry
out a bubble point flash calculation at a specified temperature.
Specify the temperature and the flash calculation
Type the first temperature, say 250K, in the text box next to temperature in the
input conditions section
The reported pressure is the saturated vapour pressure at 250K, the other
properties are listed below the phase equilibrium output. As we are dealing with
a pure component exactly the same results would be obtained if we had specified
a dew point flash at the same temperature.
The next temperature should be entered in the text box in the Conditions section
and the bubble point flash repeated at this temperature.
158 Case studies - Pure component data User Guide for Multiflash for Windows
To write a problem setup file yourself, use the file shown as an example or save
the problem you have specified interactively
As we are dealing with a single component this will be the only choice available
so making sure it is highlighted. Select a property in the list of Select property,
click on Edit to view or change the property. You can also print the properties
in the results window by clicking Write to Output. This output can then can be
saved or copied into other files.
show components "OCTANE" data ;
1 OCTANE
MOLECULARWEIGHT 114.23 g/mol
TCRIT 569.32 K
PCRIT 2.49700E+06 Pa
VCRIT 4.86296E-04 m3/mol
ACENTRICFACTOR .39690
ACENT2
TBOIL 398.82 K
HFORMATION -2.08447E+05 J/mol
SSTANDARD 466.73 J/mol/K
TMELT 216.37 K
HMELT 20740. J/mol
SMELT J/mol/K
CPMELT 50.008 J/mol/K
VMELT 1.96794E-05 m3/mol
RUNIQUAC 5.8486
QUNIQUAC 4.9360
User Guide for Multiflash for Windows Case studies - Pure component data 159
THLWATER K
VHLWATER m3/mol
DIPOLEMOMENT .00000 debye
PARACHOR 351.40 (dyn cm-1)1/4 cm3/mol
RADGYR 4.68040E-10 m
HOCASS .00000
GFORMATION 16000. J/mol
TTRIPLE 216.38 K
PTRIPLE 2.1083 Pa
HCOMBUSTION -5.07415E+06 J/mol
V25 1.63374E-04 m3/mol
SOLUPAR 15448. (J/m3)1/2
SOLIDSOLUPAR (J/m3)1/2
ZCRIT .25877
REFRACTINDEX 1.3951
TFLASH 286.00 K
TAUTO 479.00 K
FLAMLOWER .80000 vol %
FLAMUPPER 6.5000 vol %
SPGRAVITY .70662
EXPANSIVITY 1/K
OMASCALE
OMBSCALE
CNUMBER
REFVISCOSITY Pas
HYDOC
HYD1
HYD2
HYD3
ASSBETA
ASSEPSILON J/m
ASSGAMMA
ASSDELTA 1/K
ASSFF
ASSAC J m3/(mol)2
ASSBC m3/mol
ASSKAPPA
SAFTKAPPA
SAFTEPSILON K
SAFTGAMMA
SAFTFF
SAFTEK 242.78 K
SAFTSIGMA 3.83730E-10 m
SAFTLAMBDA
SAFTM 3.8176 1/mol
EOSC
LJEVISC J/K
LJBVISC m
TYPE 1.0000
COMPREFNO 93.000
CPIDEAL 1.0000 -32384. -3721.4 4.0000
76.000 290.00 -1.3945 5.6330
-5.7710 .00000 . 00000 10000.
PSAT 3.0000 -7.9121 1.3801 -3.804
-4.5013 260.00 568.95
HVAP 1.0000 54909. .37750 .00000
.00000 .00000 .00000 568.38
LDENS 1.0000 2032.5 5407.6 .00000
568.38
LVISC 2.0000 -20.463 1497.4 1.3790
.00000 .00000 216.38 398.83
VVISC 1.0000 3.11910E-08 .92925 55.092
.00000 216.38 1000.0
LTHCOND 5.0000 .21560 -2.94830E-04 .00000
.00000 .00000 216.38 398.83
VTHCOND 1.0000 -8758.0 .84480 -2.71210E+10
.00000 339.00 1000.0
STENSION 1.0000 5.27890E-02 1.2323 .00000
.00000 .00000 216.38 568.70
CPLIQUID 5.0000 224.83 -.1866 9.5891E-04
.00000 .00000 216.38 460.00
SDENS 5.0000 8340.9 -3.1515 .00000
.00000 .00000 133.15 216.38
160 Case studies - Pure component data User Guide for Multiflash for Windows
CPSOLID 5.0000 -24.000 1.9472 -8.53600E-03
1.34000E-05 2.09400E-08 20.000 216.37
VIRIALCOEFF 1.0000 2.73900E-04 -5.65219E-04
-3.63347E-04 -1.16166E-05 2.58796E-06
284.38 1500.0
CARNUMBER 000111-65-9
FORMULA C8H18
FAMILYCODE AA
UNIFAC CH3 2 CH2 6
The output includes the pure component constant properties and the coefficients
for the temperature dependent property correlations. The definitions of the pure
component correlations are given in the Multiflash Programmers Guide.
Excel interface
The current version of Multiflash does not include options for tabular output or
for producing graphical output for properties other than phase boundaries. If this
is important to you then we would recommend our Excel interface. For
example, the octane.mfl file was used in conjunction with this interface and
Excel to produce the following output for octane.
Liquid properties on the saturation line
User Guide for Multiflash for Windows Case studies - Pure component data 161
425 252.077 28039.119 3533624 7.65E-06 0.022801
450 263.577 34485.547 3741485 8.12E-06 0.025336
475 274.711 41214.916 3949345 8.58E-06 0.027994
500 285.473 48217.999 4157205 9.05E-06 0.030772
162 Case studies - Pure component data User Guide for Multiflash for Windows
Case studies - Phase equilibria
Introduction
The main purpose of Multiflash is to determine the phase equilibria and
thermodynamic properties of complex mixtures. The simple tutorial shown
earlier, see Simple Tutorial on page 19. was based on calculating the phase
equilibria of a binary hydrocarbon system. Here we will look at a more complex
hydrocarbon system and the phase equilibria of a polar mixture.
Finally, click on OK in the message box and Close in the Model set dialogue
box.
Specify the components
User Guide for Multiflash for Windows Case studies - Phase equilibria 163
The INFODATA databank will be the default data source and this is acceptable
for this case study, so we can move directly to specifying the components. You
can activate the Select Components dialogue box by either
The various methods for selecting or searching for components have been shown
before see Selecting components on page 87. As our current system contains
simple well known compounds they have been selected by
Highlighting the Name option button
Typing the component name in the Enter name text box
and pressing the enter key after the name to load it for Multiflash
or
Clicking on Add to load the component.
Click on Close to load the components
Define the composition
Click on Compositions in the Conditions section, and
Type in the compositions in the drop down table. For our example they are:
Methane 0.45
Ethane 0.20
Propane 0.10
Butane 0.10
Hexane 0.10
Decane 0.05
164 Case studies - Phase equilibria User Guide for Multiflash for Windows
To change the pressure units, click on the Select input and output units
button , then in the Tab control click on Pressure and click in the Output
option button box against bar. (You can also change the input units for pressure
if you wish.)
Having specified the model, components, compositions and units,
Enter the first temperature, 250K, in the Conditions section and
User Guide for Multiflash for Windows Case studies - Phase equilibria 165
a phase fraction of 1.0 in the text box and click on the Upper retrograde type of
solution. This fixedphase flash simulates a dew point calculation.
Click on Do flash.
The calculated dew point pressure is now 114.5 bar for the retrograde region,
whereas for the normal dew point the calculated pressure was 28.18 bar. This
confirms that we have a retrograde region for this system.
To calculate the full dew point curve you therefore need to increase the
temperature at 1K intervals above 460K, using the normal T, dew point flash,
until you meet the first convergence failure, at which point you are just beyond
the cricondenbar. You should now switch to fixedphase fraction flashes at fixed
temperature, set the options as described and reduce the temperature in small
steps. This will define the retrograde dew point curve to 405K.
Phase envelope
The same problem can be investigated more easily using the phase envelope
calculator. Set up the problem as before, but instead of carrying out individual
dew and bubble point calculations
Select Calculate/Phase Envelope or click on the Phase Envelope button
Click on V/L Autoplot and Click on Yes when the message box appears asking
if more points should be calculated. The resulting plot includes the dew and
bubble point lines and the critical point is labelled.
The output in the results window will allow you do identify the critical point
explicitly
166 Case studies - Phase equilibria User Guide for Multiflash for Windows
53C 402.713 147.11
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.
User Guide for Multiflash for Windows Case studies - Phase equilibria 167
Including a petroleum fraction
The heaviest component in our hydrocarbon stream is decane, but often the
heavier end of oil or gas condensate systems is defined as a petroleum fraction
rather than as a single specified component. Each petroleum fraction will consist
of a mixture of components and the fraction as a whole will be defined in terms
of its molecular weight, density and possibly boiling point, although the first two
properties are the most likely to be reported. Often the heavy end will be
reported as a single fraction, e.g. C7+, although sometimes a more detailed
analysis may be available breaking the heavy end down into several fractions.
Multiflash includes petroleum fraction correlations which may be used to predict
the thermodynamic and transport properties of the fraction based on the data
available, see Calculating petroleum fraction properties on page 118 .
For this case study we will remove decane and water from our stream and
replace decane with a petroleum fraction of molecular weight 234 and specific
gravity 0.838.
To delete components
Assuming the stream definition for the last case study is loaded
Click on Select components button
In the Select Components dialogue box, select water in the list of components
selected for Multiflash, then click on Delete. This will remove water from the
list. Repeat this for decane. You should now be left with methane, ethane,
propane, butane and hexane.
To add the petroleum fraction
In the Select components dialogue box
Click on the arrow to the right of the Data source list box, then select
Petroleum fractions correlations.
In the dialogue box then activated:
Enter C7+ in the Name box, enter 234 for Molecular Weight and enter
0.838 for specific gravity.
168 Case studies - Phase equilibria User Guide for Multiflash for Windows
Click on Add to include the fraction in the defined stream.
Alternatively you could use the Replace option to replace decane with C7+.
Click on Close
In the main window click on Composition and enter 0.05 for the amount of
C7+.
The petroleum fraction is now included in the stream definition and the phase
envelope calculation may be repeated with the new stream, although the
cricondenbar, cricondentherm and retrograde regions will now be different.
If you only know that the petroleum fraction is C7+ but do not have a reported
MW or specific gravity you can simply fill in 7 as the Carbon number
and Multiflash will determine the properties from a set of standard tables.
Methane 0.45
Ethane 0.20
Propane 0.10
Butane 0.10
User Guide for Multiflash for Windows Case studies - Phase equilibria 169
Hexane 0.10
Decane 0.05
we must initially carry out a P,T flash at the upstream conditions to determine
the enthalpy and then a P,H flash at the exit pressure.
Having loaded the model set and stream information
Enter the upstream temperature, 300K and pressure, 50 bar
Click on the P,T flash button
The calculated total enthalpy is -10932 J/mol
170 Case studies - Phase equilibria User Guide for Multiflash for Windows
You can also add the isenthalpic boundary for -10932 J/mol to your phase
envelope.
PVT Analysis
Many users will receive a PVT Analysis of the composition of an oil or gas from
one of the PVT laboratories and wish to use this as input to Multiflash. These
reports follow a fairly standard format and the PVT Lab Analysis form
endeavours to reproduce this to make entering information as easy as possible.
The facility to add or delete components from the generated list is also useful.
The form is discussed in detail in section PVT Analysis on page 110.
The case study we are considering here is based on a problem setup file called
pvt1_new.mfl, which uses the Revised Analysis method.
To enter a PVT Analysis either choose the Select/PVT Lab Input menu option or
click on the icon. The Lab Analysis form will then be displayed.
User Guide for Multiflash for Windows Case studies - Phase equilibria 171
Initially we will consider a case where you only have a single fluid composition.
First select the datasource for your discrete (i.e. well-defined) pure components.
This can be Infodata or DIPPR and we have chosen Infodata. Next at the top of
the column headed Single fluid choose either mass or mol % as appropriate by
clicking on the down arrow. If your PVT report offers a choice of mole or mass
% it is the mass % that is the experimentally measured data and should be given
preference for separator oils. Next enter the compositions of the discrete
components and the compositions of the petroleum cuts. In the form the
pseudocomponents or single carbon number (SCN) cuts are labelled C6, C7 etc.
In your PVT Laboratory report they may be referred to as hexanes, heptanes etc.,
with the heaviest being labelled as a plus fraction such as C20+ or eicosanes+.
In our example the heaviest SCN is C20.
The overall percentage will be totalled as you enter the compositions. If the final
total is not 100 you will be offered the opportunity to normalise the compositions
when you characterise the fluid.
You can enter further information to define the stream, such as the molecular
weight of the Stock Tank Oil (STO), the total fluid or the heaviest SCN or the
specific gravity of either the heaviest SCN or the STO. We have provided
general advice on when such data should be supplied in Fluid composition on
page 113. As the fluid in question has a heavy end (C6+) which comprises more
than 50% of the stream we should supply this information if possible. We have
therefore entered the molecular weight of the heaviest SCN but if you have the
molecular weight of the total fluid available this may be preferable as this is
again the measured quantity.
We will use the default distribution method, Infoanal2.
You are now ready to define the basis of your characterisation by choosing
where in your existing analysis you want to start redistributing the remaining
fluid into new pseudocomponents and how many pseudocomponents you want
to split this heavy end into. Weve started with the simplest case where we have
chosen to start the split at the heaviest SCN and only allocate one
pseudocomponent. Effectively we are only allocating physical properties to the
existing SCNs. Click on the Do Characterisation button and you will see a
message box such as
172 Case studies - Phase equilibria User Guide for Multiflash for Windows
followed by a screenshot of the experimental data and the fitted distribution
Click on OK and Close to return to the main window where the new fluid
composition will be reported
User Guide for Multiflash for Windows Case studies - Phase equilibria 173
You can investigate various aspects of the characterisation and the sensitivity of
the phase envelope to changing these. For instance you can change the
distribution method to Infoanal1 and re-plot the phase envelope, do this and also
include a n-paraffin distribution by ticking the Estimate Wax Content box. In
the latter case the names and compositions of the fraction custs will differ,
If you return to the PVT Lab Analysis form and instead of the heaviest SCN
choose total liquid and enter a MW of 68. Do the characterisation and plot the
phase envelope. Then see what the effect is of extending the heaviest SCN to
further fractions, by leaving C20 as the start of the pseudocomponents but
choosing to split it into 5 pseudocomponents. Alternatively you can group the
components by starting the pseudocomponent split at C8 and grouping the plus
174 Case studies - Phase equilibria User Guide for Multiflash for Windows
fraction into 15 pseudocomponents. You can see that this alters the cricondenbar
but the major effect is on the cricondentherm.
Next, return to the original fluid definition and re-plot the phase envelope, then
in the PVT Analysis form enter a watercut. This is defined in terms of the
volume percentage of the total fluid that is water. In this case choose 3 %. In
the main window plot the new phase envelope and the water phase. boundary.
Finally, return to the original fluid analysis again and this time add a separator
gas. Here we will look at a simple problem where the gas is 100 % methane
added at a GOR of 100 m3/m3. Move to the Liquid + Gas tab and enter 100 next
to methane in the left hand column headed separator gas and in the Recombined
fluid section of the PVT form set the GOR units to m3/m3 and enter 100. Do the
characterisation and return to the main window and plot the new phase envelope.
User Guide for Multiflash for Windows Case studies - Phase equilibria 175
Black Oil Analysis
The black oil analysis offers the user an opportunity to take a very limited input
specification (known as Black Oil input) for a condensate or oil and from this
generate a normal compositional analysis. Our example is based on the
blackoil.mfl file.
The minimum required input is the gas gravity(relative to air), the STO specific
gravity(relative to water) at 60F and 14.7 psi and the solution GOR. The latter
is the volume of gas produced at surface standard conditions divided by the
volume of oil entering the stock tank at standard conditions. It is often referred
to as Rs.
The remainder of the form is the standard PVT except that you do not provide
molecular weight or specific gravity. You can choose the pseudocomponent
distribution as normal, depending on the final application. In this case the split
is five fractions from C6+. Clicking on Do Characterisation generates the
message that the characerisation has been successfullycompleted in this case
there is no compositional information to generate the compositional plot. The
new composition is echoed in the main window and the phase envelope can be
plotted as before.
176 Case studies - Phase equilibria User Guide for Multiflash for Windows
Additional data can be added such as the Watson K-factor and/or the Gas
analysis. Plotting the phase envelopes shows the effect of including this data.
Refrigerant mixtures
Several of our customers have used Multiflash to determine the properties of
refrigerants. A number of pure refrigerants were added to our INFODATA
databank several years ago and more recently in our CSM model. We have also
fitted data for a large number of refrigerant mixtures and the BIPs have been
stored in the INFOBIPS databank. For mixtures we have used the RKSA model
to determine the thermodynamic properties of the mixture except for the liquid
volume/density which is calculated using the ideal solution model. This model
combination has been included in a model configuration file called refrig.mfc.
To determine the properties of any refrigerant mixture, first load refrig.mfc using
File/Load problem setup. The refrigerant mixture can then be defined as normal
using Select Components and providing the composition. However, there are
several well defined refrigerant mixtures which have been allocated refrigerant
numbers e.g. R407A. This is a mixture of the pure refrigerants, R32, R125 and
R134A, with a fixed composition (in mass percentages) of 20/40/40. To help
our users we have set up .mfl files defining components/compositions for
R401A
R401B
User Guide for Multiflash for Windows Case studies - Phase equilibria 177
R401C
R402A
R402B
R404A
R405A
R406A
R407A
R407B
R407C
R407D
R407E
R408A
R409A
R410A
R411A
R411B
R414B
R500
R501
R502
R503
R504
R507A
R508A
R508B
178 Case studies - Phase equilibria User Guide for Multiflash for Windows
Polar systems
Multiflash is equally applicable to polar mixtures, although for systems of this
type an activity model, such as Wilson-E, NRTL, UNIQUAC or UNIFAC, plus
binary interaction parameters is usually needed to obtain accurate results. For
the first three models, Multiflash has BIPs available for many binary pairs but
where these are missing you need to supply them. For UNIFAC BIPs are
generated from group structure. Before carrying out phase equilibrium
calculations for polar streams using an activity coefficient model we recommend
that you check the availability of BIPs for your system and look up interaction
parameters for the binary pairs where none are available from INFOBIPs. An
alternative is to fit experimental data to a model used in Multiflash or generate
data from UNIFAC and fit this to the model of your choice. We have provided
sample spreadsheets which allow you to do both using the Excel interface.
Reference: Dechema A good source of experimental data and BIPs is the series of volumes in the
Chemistry Data Series Chemistry Data Series, published by Dechema. The UNIFAC model will
provide estimates of vapour-liquid and liquid-liquid equilibria without the need
Vols I to XIV, Dechema
for BIPs.
User Guide for Multiflash for Windows Case studies - Phase equilibria 179
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.
180 Case studies - Phase equilibria User Guide for Multiflash for Windows
Entering BIPs
You may have a mixture where there are no stored BIPs. Take for
example the system acetone/hexane. If your repeat the earlier
steps to select components, units and models and again look at
the BIPs using the Tools options you will see that for the WilsonE
model no BIPs are available.
Click on the P, Bubble point flash button to see the model prediction using the
default, BIPs = 0.0.
For a mixture of 0.314 mole acetone and 0.618 mole the predicted result is a
bubble point pressure at 40 degC of 311.6 mmHg and a vapour phase fraction of
acetone of 0.3951. The experimental data is 510.8 mmHg with y =0.5485.
However, for this data set Dechema recommends BIPs for acetone/hexane for
the WilsonE model of 1067 and 326.8 cal/mol. Multiflash recognises BIPs in SI
units therefore you must convert these to J/mol, resulting in values of 4460 and
1366 respectively. You enter these values into Multiflash using the Tools /BIPs
from the menu bar.
Select Tools, then select BIPs
In the Show BIP values box highlight WILSONBIP2 and click on Edit
Remember to convert the WilsonBIP2 is the name recognised by Multiflash for BIPs relating to the
units from the Dechema data Wilson E model. This model has two, which may be expressed as constant,
series to the correct input linear or quadratic functions of temperature. The Dechema BIPs are
units for Multiflash temperature independent, i.e. constant. The BIPs are asymmetric and not
interchangeable. It is therefore important that if the BIP values are reported for
acetone as component 1, then the binary pair is entered with acetone as the first
component.
Enter the new BIPs
User Guide for Multiflash for Windows Case studies - Phase equilibria 181
Select the new model set, this will clear the previous model and BIPs, but
retain the components, compositions and units.
Calculate the P, bubble point without BIPs
Remember NRTL has 3 Enter BIPs, as given in the table below (in J/mol), using the Tools/BIPs option.
constant coefficients, not 2: The bipset names are the model name followed by BIP, e.g. NRTLBIP3,
two asymmetric and one UNIQUACBIP2. BIPs are not required for UNIFAC as they are generated from
symmetric group contributions.
Calculate the bubble point pressure again. with the BIPs.
You should reproduce the following results.
Pressure mmHg y1
Wilson E No BIPs 311.6 0.3951
BIPs: 4460, 1366 511 0.5532
You can see from the results the importance of using interaction parameters for
non-ideal systems. All the calculations were carried out with the ideal model for
the vapour phase. For this sytem using the Virial (HOC) model, or RK for the
vapour phase model does not give significant differences. However, for some
components, such as acetic acid which may dimerise, using the Virial (HOC)
model would be beneficial.
You could also enter different BIPs for this system from the Dechema series and
examine the sensitivity of the results to these variations.
Liquid-liquid equilibria
Many non-ideal polar systems exhibit liquid-liquid equilibria. To model these
systems you must choose an activity model capable of predicting two liquid
phases, the Wilson model cannot do this.
Two suitable models are UNIQUAC LLE and NRTL LLE. The LLE version of
NRTL usually has the parameter set to 0.2 by default. Again to obtain
realistic results you should enter BIPs and we have incorporated BIP data for
over 300 systems into our INFOLLBIPs databank. If you take UNIQUAC or
NRTL parameters taken from the Dechema Chemistry data Series they must be
multiplied by the gas constant (8.314 JK-1mol-1) before being entered.
A typical mixture which exhibits liquid/liquid behaviour is butanol/water
Dechema Chemistry Data Series. Volume V, Part 1, page 236.
If you have set up a problem with only one gas and one liquid phase defined you
may see a warning message above a vapour-liquid or one liquid phase solution.
Flash at fixed P and T:
*** WARNING -20001 ***
Unstable solution, more phases exist.
T =298.25K P=1.00000E+05Pa ? CONVERGED ..UNSTABLE
182 Case studies - Phase equilibria User Guide for Multiflash for Windows
This instability warning indicates that you should consider looking for another
liquid phase, and define a second phase descriptor for this. Use the Select Model
Sets, or the model configuration files provided for activity methods, to ensure
that two liquid phases are available.
To carry out the case study in Multiflash
Select the UNIQUAC LLE model
Select butanol and water from INFODATA
Set the butanol composition to .5 mol, methanol and water to 0.50.
You can check that BIPs are available using the Tools/BIP
option.
Set the temperature to 298.15K and the pressure to 1e5 Pa.
Carry out a P,T flash.
The mixture will be a single liquid phase.
If you increase the water concentration to 0.7 with 0.3 mole butanol and repeat
the two phase flash you get a liquid-liquid solution.
Vapour-liquid-liquid equilibria
The situation is a little more complicated if you have VLLE. None of the
activity models which can handle VLLE do this well without specific tuning of
the BIPs. The VLE variants of UNIQUAC and NRTL are configured to be used
with GAS and Liquid1 and the LLE variants with Liquid1 and Liquid2. To
calculate VLLE with either you must first "Switch-on" the missing phase. The
only difference is the source of BIPs and we have increased the options by
allowing two BIP databanks to be in force at any time. The LLE model options
are configured to first search INFOLLBIPs, then to supplement any missing
BIPs from INFOBIPs. The VLE variants are configured only to search
INFOBIPs. For VLLE it may therefore be prefferable to use the LLE model
variant. However, it is difficult to make an absolute recommendation, trying
both approaches and assessing the differences might be useful. You can also add
INFOLLBIPS to a VLE variant using Tools/Command and entering
bipdata INFOBIPS INFOLLBIPS;
Azeotropes
You can use Multiflash to identify azeotropes; the temperature and pressure
where the composition of the liquid and gas phase are identical. They can be
investigated by carrying out a series of flash calculations but this is time-
consuming. For binary azeotropes you might wish to consider using the Excel
interface. Below is a plot of gas phase versus liquid phase composition for the
propanol water system using Excel. The azeotrope is clearly identified at a mole
fraction of 0.42 propanol.
User Guide for Multiflash for Windows Case studies - Phase equilibria 183
Propanol - Water
1
0.9
0.8
0.7
y,propanol
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.2 0.4 0.6 0.8 1
x, propanol
You can vary the pressure or temperature and see the effect on the azeotropic
point, or investigate the effect of adding a third component.
Eutectics
Similarly, you can use Multiflash to determine a eutectic, although again this is
mostly easily seen using an Excel spreadsheet. An example would be a mixture
of benzene and napthalene. In addition to defining a fluid phase model, for
example RKSA, you also need to allocate the freeze-out model to each
component. Using the Multiflash functions in Excel you then carry out a series
of calculations to identify, for a given pressure, the temperature at which solid
benzene and solid naphthalene forms. A plot of the predicted temperature versus
composition for both shows the eutectic point. For the RKSA fkuid phase model
and 1 bar this is predicted to be at 296.3K and a mole fraction of benzene of
.8626. The recently added Regular Solution model could also be used for this
particular mixture. For this fluid phase model the predicted eutectic at 1 bar is
296.4K and .8638 mole fraction of benzene. As the plot below shows the results
for the models are virtually indistinguishable.
Benzene-Naphthalene eutectic
370.00
350.00
330.00
T/K
310.00
290.00
270.00
250.00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x Benzene
184 Case studies - Phase equilibria User Guide for Multiflash for Windows
Polymers
The inclusion of the PC-SAFT equation of state in Multiflash 3.3 has extended
Multiflash applications to the calculation of the phase behaviour of polymers,
solvents and gases. PC-SAFT is a complex equation and to be able to develop a
robust implementation capable of predicting multiple phases is unusual. Owing
to the high molecular weight, and correspondingly low mole fractions, of
polymers in solution considerable effort has gone into improving the phase
algorithms in Multiflash, but we are aware that further improvements may be
necessary.
Data input
It will not be apparent to the user, but we have re-structured the pure component
databanks to provide a more flexible structure. This will allow storage of the
data required for new models, such as PC-SAFT. Although we have made these
changes in Multiflash 3.3 we have not yet included any data for polymer
components. At present these need to be created using the Multiflash User
Defined component route (Select/Components) and either saved as part of a
complete .mfl file or a partial file containing the polymer data only.
The required input data are:
Critical temperature (TCRIT), critical pressure (PCRIT), acentric factor
(ACENTRICFACTOR),
PC-SAFT parameters (SAFTEK, SAFTSIGMA, SAFTM, SAFTKAPPA,
SAFTEPSILON, SAFTFF)
Ideal gas Cp (CPIDEAL).
Users should note that TCRIT, PCRIT and ACENTRICFACTOR are necessary
to generate starting values for flash calculations but do not affect the computed
results from PC-SAFT. Also SAFTKAPPA, SAFTEPSILON and SAFTFF are
only needed for associating components.
If your system is polydisperse, i.e. has the same polymer but with a range of
molecularweight, then you can enter several polymers with varying properties,
each called by a different name. This is analogous to setting up different
petroleum fractions, although we do not yet have a facility to help the user set up
the data for polymers.
Polymers are not well defined chemical compounds but rather a distribution of
chain molecules of varying molecular weight. In Multiflash, polymers must be
represented by one or more pseudocomponents which must be set up as user-
defined components.
Using PC-SAFT, every pseudocomponent for a given polymer must be assigned
the same values of the pure-compound parameters SAFTSIGMA (in metres, not
ngstrom units) and SAFTEK. In addition, the SAFTM parameter must be
specified. This is normally quoted as a ratio to the molecular weight, so it has to
be calculated for each polymer pseudocomponent knowing the molecular weight.
For polystyrene, for example, Gross and Sadowski give the ratio as 0.019, so for
a polystyrene pseudocomponent of molecular weight 100000, the SAFTM
parameter should be set to 1000000.019=1900, etc.
Our example polymer.mfl describes a simple binary of polystyrene plus butane.
The required properties of polystyrene are included in the input file, as are the
pure component SAFT parameters for butane. Load the input file in the normal
way and carry out a P,T flash at the input conditions supplied. The results show
a liquid-liquid split as expected.
User Guide for Multiflash for Windows Case studies - Phase equilibria 185
You can also carry other flashes, such as a bubble point calculation
186 Case studies - Phase equilibria User Guide for Multiflash for Windows
The series of papers by Sadowski et al, detailed in the "Models and Physical
Properties Guide, are a useful source of input parameters for PC-SAFT for
several polymers.
Until the advent of PC-SAFT, Flory-Huggins was sometimes used for polymer
calculations. This is still possible but not recommended. To apply the Flory
Huggins model, in addition to the critical parameters required by the Multiflash
algorithms the additional data needed are: vapour pressure (PSAT), saturated
liquid density (LDENS), solubility parameter (SOLUPAR) and molar volume at
25C (V25).
Estimated properties have been included in the file polymer3.mfl for polystyrene
and the predicted bubble point for the polystyrene-butane binary shown below.
User Guide for Multiflash for Windows Case studies - Phase equilibria 187
Case studies - Hydrate
dissociation, formation and
inhibition
Introduction
This section is only applicable if your copy of Multiflash includes the hydrates
option.
Natural gas hydrates are solid ice-like compounds of water and the light
components of natural gas. Also, some heavier hydrocarbons found in gas
condensates and oils are now known to form hydrates if smaller molecules such
as methane or nitrogen are present to stabilise the structure. Hydrates may form
at temperatures above the ice point and are therefore a serious concern in oil and
gas processing operations. The phase behaviour of systems involving hydrates
can be very complex because up to seven phases must normally be considered.
The behaviour is particularly complex if there is significant mutual solubility
between phases, e.g. when inhibitors or CO2 are present. Multiflash offers a
powerful set of thermodynamic models and calculation techniques for modelling
gas hydrates.
The models used in Multiflash for hydrates and hydrate inhibition have been
briefly described, see Hydrate model on page 55 or our separate guide to
models and physical properties.. Components known to form hydrates are also
listed.
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 189
conjunction with one of the solid phases such as any hydrate phase or the ice
phase. Therefore the selection of Phase Nucleation does not increase the number
of phases associated with the model used.
The hydrate model sets and the hydrate model configuration files have the
following definitions.
Hydrate model
The thermodynamic hydrate model consists of lattice parameters for the empty
hydrate and parameters for the interaction of gas molecules with water in the
hydrate. There are different parameter values for each hydrate structure, Hydrate
1, 2 and H. In addition the hydrate must be associated with a liquid phase model
that is used to obtain the properties of water. It is important that this is the same
model that is used for water as a fluid phase.
Nucleation model
This model can be used to predict the nucleation of any hydrate phases and
provides an estimate of the temperature or pressure at which hydrates can be
realistically expected to form. The nucleation model is based on the statistical
theory of nucleation in multicomponent systems.
With the Infochem hydrate model described above and the nucleation model, the
hydrate formation and dissociation boundaries can be predicted. Between these
two boundaries is the area of hydrate risk.
Ice model
Ice is treated as a pure solid phase. The Infochem freeze-out model can be used
to model the solidification of any component. As with the hydrate phase it is
necessary to associate the solid phase model with a liquid phase model that is
used to obtain the properties of water. It is important that this is the same liquid
model that is associated with the hydrate phase. The nucleation model can also
be used to predict the temperature or pressure at which ice starts to nucleate.
Phases
In most cases six phase descriptors (PDs) are required: gas, hydrocarbon liquid,
aqueous liquid, hydrate 1, hydrate 2 and ice. At high pressures and/or low
temperatures the gas phase may become liquid-like and a second non-aqueous
liquid PD is needed. This is also the case if there is a significant amount of CO2
or H2S present. When considering structure H hydrates an additional phase
descriptor is needed for hydrate H.
190 Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
In most practical cases a natural gas contains propane and the stable hydrate
structure will be hydrate 2, although for very lean gases at higher pressures
hydrate 2 may be the most stable form. Key components are defined to
distinguish between the hydrocarbon and aqueous liquid phases.
The phase names used in the hydrate models are: GAS, LIQUID1, LIQUID2,
Water, Ice, HYDRATE1, HYDRATE2 and HYDRATEH. You can apply Phase
Nucleation to any of the solid phases (hydrates or ice) defined by the hydrate
model. If Phase Nucleation is selected, this means that the nucleation model is
defined and can be used to predict the nucleation of any of the hydrate phases or
ice.
In contrast to the thermodynamic hydrate model which allows all possible phases
to be present when carrying out calculations, the nucleation model considers
only the nucleation of the specified phase. At low pressures this can lead to
predictions that the hydrate formation temperature is higher than the dissociation
temperature. However, this is not a real situation as ice is not being allowed to
form.
1000
LH critical point
100
hydrocarbon VLW
phase envelope
hydrate line
Press/bar
VLI
VW V
1
VI
ice line
0.1
150 200 250 300 350 400 450 500 550
Temp/K
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 191
Will hydrates form at given P and T ?
To find out whether a mixture will start to form hydrates at a given pressure and
temperature it is simply necessary to define your mixture, specify a hydrate
model set and do a P, T flash. If you wish to start from a problem setup file we
have provided hyd1.mfl
To define the case study interactively:
Select Select, then select Model Set, followed by selecting Hydrates tab to
activate the Hydrates dialog box. In the dialog box, select the relevant phases
required and initially specify RKSA (Infochem) as the fluid phase model.
Click on OK once the hydrate model set has been successfully defined and
loaded.
Specifying the components and composition
We will use a simple binary mixture plus water for this case study, but in
practice it is common to calculate hydrate dissociation and inhibition with large
multicomponent streams including several petroleum fractions. The mixture
chosen consists of 0.5 mol methane, 0.5 mol butane plus water.
Define the components in the usual way; click on the Select components
button, enter the component name in the Enter name text box and press the
enter key or click on Add to select them for loading into Multiflash. Click on
Close
Click on composition and enter the correct number of moles for each
component. Add 1.0 mol of water.
Enter the temperature, 250K and the pressure, 10 bar (remember to change the
standard pressure units from Pa to bar)
Click on the P,T flash button
You will see the following results in the results window.
192 Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
Hydrate 2 is formed at the specified conditions, and you can see that this is in
agreement with the phase diagram. Note that the output shows the amount of
hydrate formed just as it does for other phases.
P
H y d r a te z o n e H y d ra te H y d rate free
r risk
e
s
s
u
r H y d r a te f o r m a ti o n c u r v e H y d r a te d i s s o c i a ti o n c u r v e
e
T e m p e r a t u r e
hydrate will form. Between these two points is the area of hydrate risk where
hydrates may or may not form depending on the time scale.
To calculate the hydrate dissociation temperature at given pressure
Retain the pressure at 10 bar
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 193
Click on Do flash
The results,
show that the hydrate first begins to form at 273.236K. It is important to specify
the correct hydrate structure to search for. If Hydrate1 was specified in the
above example the calculation would fail because there is no solution where
hydrate1 is more stable than hydrate2. In most cases of practical interest
hydrate2 is the structure formed, although hydrate1 may be more stable at high
pressures for streams containing a high concentration of methane or H2S. If
hydrate1 is more stable and if there are enough components present in the
mixture, hydrate1 should be present in non-zero amount in the list of phases
formed. If in doubt you can check with the P,T flash option which reports which
structure is stable.
194 Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
The calculated results with the nucleation model are displayed in the main
screen. Note that the hydrate formation temperature at 10 bar is now 263.42K,
about 10 Kelvin lower than the hydrate dissociation temperature, 273.2K.
If you try to calculate the hydrate formation temperature without first defining
the nucleation model, then the calculation will not converge and error messages
will occur in the screen:
The hydrate first forms at 3.6 bar. Under these conditions the hydrate forms from
the ice phase rather than the liquid water phase. The hydrate formation pressure
at the same temperature is 0.783 bar.
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 195
Hydrate phase boundary
You can also use the phase envelope calculator to plot the hydrate phase
boundaries for formation and dissociation for this stream by using the
thermodynamic hydrate model and nucleation model.
You will notice that at low pressures hydrate formation apparently occurs at
higher temperatures than hydrate dissociation. You are referred to Phases on
page 205 for a discussion on the reasons for this.
196 Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
For a water tolerance calculation this would be pure water. The fixedphase
and phase fraction can be specified using the Select phase and Enter phase
fraction boxes, zero molar phase fraction of hydrate2 in this case. The
tolerance calculation combines the two mixtures in different ratios
until the specified condition is met. The following example finds the maximum
water content for the above mixture at 250K and 10bar.
As the overall composition must be specified on a water free basis, first remove
water from the mixture by:
Clicking on Composition and entering 0.0 for the amount of water. Water
must remain in the components list.
Select Calculate from the menu bar, then select Tolerance Calculation.
Select the required phase from Select phase box by clicking the downward-
arrow on the right side of the box, then set phase fraction to zero in Enter phase
fraction box.
Click the Composition of Second Fluid tab to obtain the second stream of the
mixture, then set the composition of water to 1.0 mole and leave the rest to zero.
Click Calculate to carry out the tolerance calculation. Click Close back to the
main window.
In the results window you will see
The first column shows the overall composition at the hydrate dissociation point.
The predicted maximum water content is 38.3 PPM on a molar basis. The
amount of second fluid added is the number of moles of water specified by the
tolerance calculation which must be mixed with the original water-free stream to
meet the condition of zero hydrate phase.
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 197
list of components in the mixture and specify the amount in the total mixture just
as for any other component or you can use the Inhibitor Calculator (see
Inhibitor calculator on page 101) to add the amount of inhibitor relative to
water. However, the inhibitor will not, of course, remain solely in the water
phase but will partition between the different phases present at equilibrium and
the amount in a particular phase will depend on the conditions and the amounts
of other components. This is exactly what happens in reality.
All the calculations described above can be carried out in the presence of
inhibitors.
198 Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
The results show that even with the addition of inhibitor hydrates can still form.
However, there is now an additional free water phase which contains most of the
methanol.
You can see that, compared to the earlier calculation in the absence of methanol,
the addition of methanol has reduced the hydrate dissociation temperature from
273K to 252K. Virtually all the methanol is in the aqueous phase at these
conditions.
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 199
Amount of inhibitor required to suppress
hydrates
Multiflash can determine the amount of inhibitor that must be added to the
system at a given pressure and temperature in order to suppress hydrates. This
is another example of a tolerance calculation and is therefore
specified using the Tolerance Calculation from the Calculate menu.
The overall compositions must be specified on an inhibitor-free basis. The
inhibitor is entered as a second stream using the tolerance calculation. The
phase required to be fixed and phase fraction can be specified in the Select
phase and Enter phase fraction boxes, zero phase fraction of hydrate2 in this
case. The tolerance calculation combines the two mixtures in different ratios
until the specified condition is met. The following example finds the amount of
methanol that must be added to suppress hydrates for the above mixture at 250K
and 10bar.
Remove methanol from the main stream by clicking on Composition and
entering 0.0 mol for methanol.
Select Calculate, then Tolerance Calculation to activate the Tolerance
Calculation dialogue box.
Select the required phase from Select phase box.
Set phase fraction to zero.
Click the Composition of Second Fluid tab to specify the composition of
methanol as 1.0 mole and leave the remainder zero.
Click Calculate to carry out the tolerance calculation.
Click Close to go back to the main window.
200 Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
The first column shows the overall composition at the hydrate dissociation point.
The predicted methanol concentration required is 14.35% on a molar basis with
respect to the total stream, approximately 24.9 mol % with respect to water. The
amount of second fluid added is the number of moles of the mixture specified by
the tolerance calculation which must be mixed with the original inhibitor-free
stream to meet the condition of zero hydrate phase.
If the methanol concentration is required on a mass basis it is simple to change
the output units and recalculate the results.
Salt inhibition
Multiflash models for hydrate inhibition include the inhibiting effect of saline
water. The original salt model represents the salts as a single salt
pseudocomponent which can be loaded from INFODATA. As sodium chloride
is usually the dominant component, the model reduces other salt components to a
sodium chloride equivalent basis and the databank stores the molecular weight of
sodium chloride. The Electrolyte salt model introduced treats the salt as an
electrolyte composed of Na+ and Cl- ions. Future extensions will include
additional ions.
Unfortunately the information supplied for the amount of salt in brine, formation
or production water is not usually specified in the input format required. To help
you with the conversion we have provided a Salinity Calculator, see Salt
calculator on page 103 that converts various analyses into either the equivalent
amount of salt component or sodium and chloride ions.
To repeat the calculation for the hydrate dissociation temperature at fixed
pressure using salt, rather than methanol, inhibition:
Initially, select the RKSA(Infochem) model and 0.5 moles of methane, 0.5 moles
of butane and 1.0 moles of water as before.
Set the pressure units to bar and enter 10 bar for the pressure
Select the Inhibitor Calculator from the Tools menu and the tab for the Salt
Component Model
Enter 15 mass% NaCl in the Salt Analysis table
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 201
The Salinity Calculator will then determine that this is equivalent to adding
0.0544 mole of salt component to the 1 mole of water in the mixture.
and the salt component and this amount will be entered in the Composition drop
down table.
Specify the fixed phase flash at constant pressure, setting hydrate2 to 0.0, and
click on Do flash
The output shows that the hydrate dissociation temperature at 10 bar for this
stream is reduced from 273K to 265K.
To compare this to the results using the new salt model, return to Select
ModelSet and this time define RKSA(Infochem) + Electrolyte as the model.
Defining this model will automatically remove Salt component from the list of
components. With no salt present the hydrate dissociation temperature at 10 bar
is 273.2K, exactly the same as with RKSA(Infochem). Now from the Inhibitor
Calculator select the Electrolyte Model tab and enter 15 mass% NaCl in the Salt
202 Case studies - Hydrate dissociation, formation and inhibition User Guide for Multiflash for Windows
Analysis table. This time .0544 moles of Na+ and .0544 moles Cl- are added to
the component list. The new salt model also predicts that the hydrate
dissociation temperature at 10 bar is reduced to 265.1K. Larger differences may
occur at higher salt concentrations.
CPA model
You can repeat the above calculations using the CPA model for the fluid phase.
The chosen mixture is not one where we might expect to see significant
differences between model predictions.
The predictions of hydrate dissociation temperatures and pressures are virtually
identical. The hydrate dissociation temperature at 10 bar with RKSAINFO was
273.236K, with CPA it is 273.238K. Similarly the hydrate dissociation pressure
at 250K was 3.6092 bar with RKSAINFO and is 3.6106 bar using CPA.
The partitioning results have been improved with the CPA model and the results
are seen in the tolerance calculations. The amount of water required before
hydrates form at 250K and 10 bar changes from 3.83e-5 mol (RKSAINFO) to
4.41e-5 (CPA) and the amount of methanol required to inhibit hydrate formation
at these conditions with 1 mole water present reduces from .3352 mole
(RKSAINFO) to .3223 mole (CPA).
CPA can only be used with the new electrolyte salt model. With 15 mass%
NaCl the hydrate dissociation temperature at 10 bar is reduced to 265.1K.
User Guide for Multiflash for Windows Case studies - Hydrate dissociation, formation and inhibition 203
Case studies Wax deposition
Introduction
This section is only applicable if your copy of Multiflash includes the Wax
option.
Waxes are far more difficult to understand than pure solids because they are
complex mixtures of solid hydrocarbons that freeze out of crude oils if the
temperature is low enough. Waxes are mainly formed from normal paraffins but
isoparaffins and naphthenes are also present. As with hydrates the formation of
waxes is a serious concern in oil and gas processing.
Before discussing the modelling of wax deposition it is worth referring to a
paper by Erickson et al. SPE 26604, (1983). which compares the results of
measuring wax appearance temperatures (WAT) using three different
experimental techniques. For twelve oils, where there were measurements made
by at least two different techniques, there was only one case of complete
agreement between two methods. Otherwise the minimum difference between
techniques was 8 F, the maximum difference was 55 F, whilst the average
difference was 24 F. It appears that the accuracy of WAT measurements has
improved in recent years, but it is still difficult to measure; it is realistic when
assessing results to assume that experimental error in WAT values may amount
to several degrees.
Multisolid model
This model is associated with a model for the liquid phase, typically a cubic
equation of state. Originally we offered two fluid models from our standard
model set, RKSA and PRA but recommended the RKSA model. RKSA is now
the only fluid model accessible from the standard Model set window but the
PRA based version can still be used based on loading the waxpra.mfc file..
With the multisolid model the prediction of wax appearance temperatures is
particularly sensitive to the characterisation of the fluid; the carbon number
distribution and the properties assigned to each pseudo-component. As the PVT
Analysis facility is common to several models we have not defined the
characterisation procedure as part of the wax model, but allowed users full
flexibility. You should be aware though that your choice of where to start the
User Guide for Multiflash for Windows Case studies Wax deposition 205
pseudocomponents and the number of pseudocomponents your plus fraction is
split into can significantly affect the WAT predictions.
Our recommended procedure for the multisolid model is to start the
pseudocomponents from C6 and to split the plus fraction into 15 pseudo-
components, regardless of the experimental analysis of the distribution.
We have made every effort to include constraints and corrections that stabilise
the predictions. In general it appears from our tests that you should not split the
plusfraction into less than 5 or more than 15 pseudocomponents. Starting the
split from >C6 will usually tend to increase the predicted WAT but this will not
always be the case. Similarly, using the PRA model in place of RKSA usually
increases the WAT prediction by 3-4K.
Whatever the characterisation procedure chosen, if you have an experimental
value for the WAT you can use the matching procedure to amend the properties
of your pseudocomponents to reproduce the measured value.
206 Case studies Wax deposition User Guide for Multiflash for Windows
Select one of the models and click Define Model button to define the wax
model in the problem definition. Then Click on Close.
Go to the PVT Analysis form to characterise your fluid. The use of this is
described in detail in PVT Analysis on page 190. For the Multisolid model,
choose the Original Infonal1 method and complete the liquid composition table.
Set the Start pseudocomponents to C6 and number of pseudocomponents to 15.
Then Click on Do characterisation to characterise your fluid.
If you have selected the Coutinho model then you must choose the Revised
method (Infoanal2) for the distribution. If data are available you should provide
both the n-paraffin and other liquid hydrocarbon compositions and list these on
the "Single fluid with n-paraffins tab". You must then choose the split for both
liquid and n-paraffin distributions before completing your characterisation. If no
n-paraffin distribution is available then the liquid composition should be entered
on the Single Fluid tab and either the Total wax content enetered in the
appropriate text box or the box to estimate the wax content should be ticked.
This will activate the n-paraffin distribution and both this and the liquid
distribution should be defined before characterisation.
If you try to use a n-paraffin distribution with the Multisolid model then an error
message will be generated.
Fixed Phase Fraction Flash - at specified P (Mole
Fraction):
*** ERROR 15406 ***
The petroleum fractions are not suitable for the
Multisolid wax model.
*** ERROR 10022 ***
Model cannot be initialised
The WAT at any pressure can then be calculated by setting the pressure and
using the fixed phase fraction flash (at specified P) with Wax as the selected
phase with zero mole fraction.
User Guide for Multiflash for Windows Case studies Wax deposition 207
or the phase envelope can be used to plot the wax booundary.
Our particular example is based on a supplied problem set up file called wax.mfl.
This particular fluid has a reported WAT of 45 DegC at 1 bar. The initial
problem is set up to use the Multisolid model.
The predicted WAT at one bar is 45.6 DegC.
Now return to the model selection and this time specify the Coutinho model. In
the PVT Analysis form select the Revised analysis method (nfoanal2). Tick the
estimate wax content box and set the n-paraffin distribution to start from C6 with
15 pseudocomponents and complete the characterisation. As you are using
Infoanal2 you will also see a plot comparing the experimental andfitted SCN
distribution.
The WAT at I bar is now predicted to be 49.4 DegC. Return to the PVT analysis
and, instead of estimating the wax content, enter 8.1% as the Total wax content
and complete the characterisation. This reduces the WAT to 48 DegC.
You may wish to vary the pseudocomponent split for the Multisolid model and
the n-paraffin distribution for the Coutinho model and see the effect on the
predicted WAT.
The wax phase boundary for both models can be generated and compared using
the phase envelope plotter.
If you have a measured values for the WAT then you can tune the
pseudocomponent properties for either model to match these values. This is done
using the Tools/Matching/Other phases option. The Matching option is
described in Matching using petroleum fraction properties on page 121.
For this particular example we know the WAT at 1 bar is 45DegC.
208 Case studies Wax deposition User Guide for Multiflash for Windows
The matching facility will amend the values for the melting temperature and the
change of enthalpy on melting for all the pseudocomponents until the
experimental WAT is reproduced. The amended fraction properties are echoed
in the main window. For the Coutinho model it is the properties of the n-paraffin
fractions that are modified.
In this case we only have a sinle experimental WAT. The resultant wax phase
boundaries now show agreement at the matched WAT at 1 bar, but still exhibit
entirely different behaviour with pressure.
User Guide for Multiflash for Windows Case studies Wax deposition 209
The full range of flashes is available for the Wax models.
9.0
Coutinho model
Amounts of wax in fluid ( wt%)
8.0
Multisolid model
7.0 exp.
6.0
5.0
4.0
3.0
2.0
1.0
0.0
235 245 255 265 275 285 295 305 315
Temperature / K
210 Case studies Wax deposition User Guide for Multiflash for Windows
Case studies Asphaltene
flocculation
Introduction
One of the major problems for the oil industry is the precipitation of heavy
organics during production, transportation and the refining or processing of
crude oil. Asphaltenes are polar compounds that are stabilised in crude oil by
the presence of resins. If the oil is diluted by light hydrocarbons, the
concentration of resins goes down and a point may be reached where the
asphaltene is no longer stabilised and it flocculates to form a solid deposit.
Because the stabilising action of the resins works through the mechanism of
polar interactions, their effect becomes weaker as the temperature rises, i.e.
flocculation may occur as the temperature increases. However, as the
temperature increases further the asphaltene re-dissolves in the oil. Thus,
depending on the temperature and the composition of the oil, it is possible to find
cases where flocculation both increases and decreases with increasing
temperature.
The Infochem model for asphaltenes is based on a cubic equation of state but has
an additional term to describe the association of asphaltene molecules and their
solvation by resins. The parameters for the model have been developed from a
study of nearly thirty sets of experimental measurements of asphaltene
deposition which includes both proprietary and public domain data. The model
is complex and to ensure reliable results we recommend that you follow the
procedure we suggest until you are familiar with the model and the behaviour of
your particular fluid.
The asphaltene model in Multiflash is primarily intended for calculating
asphaltene flocculation from live oils. We are aware that many users have only
titration data for dead (STO) oils. We have investigated using this titration data
to set the asphaltene model parameters and this is discussed later in the case
study.
Input data
The ideal input data for the model are:
A compositional analysis of the live oil
The amount of asphaltene in the oil and the ratio of resin to
asphaltene, often determined from the SARA analysis
One set of flocculation conditions for the asphaltene flocculation
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 211
Bubble point (optional) to tune the petroleum fraction properties.
If a full SARA analysis is used to specify the weight % of asphaltene it is
important that it relates directly to the compositional analysis of the live oil.
Often the SARA will have been measured for the stock tank oil rather than the
total reservoir fluid. If you have the detailed compositions for separator gas and
liquid and the gas oil ratio (GOR) you should enter this data in the PVT Analysis
form for characterisation. In this case you can use the SARA as reported. If you
only have the reservoir fluid composition and the SARA from the stock tank oil
the weight % of asphaltene may be slightly in error. A quick way to correct the
weight % of asphaltene is to flash the reservoir fluid to stock tank oil conditions
and work out the mass percent of gas. In the SARA analysis add this to the
Saturates (S) text box and re-normalise the SARA when this option is offered.
For some samples you may only know the absolute weight % of asphaltenes and
resins in the total live oil but not the full SARA analysis. In these cases you can
just use the weight % of resins and asphaltenes and ignore the text boxes for
saturates and aromatics in the PVT Lab Fluid Analysis dialog box. For the
asphaltene model, the saturates and aromatics part of SARA are only used to
normalise the weight % of resins and asphaltenes.
If you do not have the complete data set we recommend we have developed
correlations to assign the required parameters. The minimum set of data in this
case are:
A compositional analysis of the live oil
Reservoir temperature
Bubble point (optional), to tune the petroleum fraction
properties.
Obviously the more data available the better the model predictions.
The prediction of asphaltene flocculation is not as sensitive to the
characterisation of the fluid as the wax models. However, we suggest you
consider using a common characterisation procedure. We recommend that in the
PVT Analysis facility you start the pseudocomponent split at C6 and split the
fraction into 15 components, regardless of the original experimental distribution.
Finally, to model asphaltene flocculation successfully you need to adjust one
model parameter to match actual flocculation data. If you have such
experimental data available then you match to this. If you do not have any data
there are two options. We have modified the screening procedure suggested by
De Boer et al to adjust the parameter based on a knowledge of the reservoir
conditions or you can use STO titration data if this is available,
212 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
The default phases for the asphaltene model are gas, liquid1 and asphaltene.
However, you can add a water phase if you wish. In Windows this can be done
very simply by ticking the water check box. In the asphalt.mfc file we have
commented out the lines defining the water phase and the key component for this
phase.
If you wish amend the .mfc file you must edit it to remove the # sign before the
relevant lines.
The next step is to characterise your fluid. Go to the PVT Analysis form,
described in detail in PVT Analysis on page 110. Initially, set the Analysis
method to the original Infoanal2 method. Enter the fluid analysis and set the
Start pseudocomponents to C6 and the number of pseudocomponents to 15.
Enter any data you have on the molecular weight and/or specific gravity.
The final step in the characterisation is to enter any data you have on the weight
of asphaltene in the oil and the ratio of resin to asphaltene. The example we are
going to look at is based on a supplied problem set up file, asphex.mfl. We have
assumed in this example that a full SARA analysis is available, but later in the
case study we will go back and look at the options if you dont have this much
data.
If you load asphex.mfl the PVT Analysis form will look like this
Once you are happy the data is correct Click on Do Characterisation. In this
case a message box will tell you the characterisation has been successfully
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 213
completed and a plot of the data and fitted diistribtion. You can then Click on
OK and on Close to go back to the main window.
If you have any warnings or errors associated with your own examples then the
relevant message box will appear. Those related to fluid characterisation in
general are described in PVT Analysis on page 110. Since the release of the
asphaltene model we have had feedback from several users. In our original
database of asphaltene measurements the resin/asphaltene ratio was always
greater than 2.5. However, some of our users have reported values below this,
possibly because the SARA analysis was based on a different experimental
techniques. Depending on the actual R/A entered you may find that model
parameters cannot be generated. We have added a warning message if R/A is
below 2.5
you can either ignore this warning message and see if model parameters can be
produced or you can delete the Resin amount from the SARA and tick the
Estimate RA box and the model will generate a default R/A ratio.
After characterisation the asphaltene component(s) are denoted by an A prefix,
e.g. AS39+, and the resin component(s) by an R prefix, e.g. R39+.
The next stage is to use the matching facility to tune the pseudocomponent
properties and fix the one adjustable model parameter. We recommend that if
you have bubble point data available you tune the petroleum fraction properties
to match this. Matching the bubble point has been incorporated into the
asphaltene matching form.
In practice we have found that you do not always have to match to bubble point
data to model the asphaltene data, although you almost always need such
matching for light oils. In this particular example bubble point data were not
provided but we have used an appropriate value for demonstration purposes.
However, we do recommend use of the matching procedure for the asphaltene
phase. Although we have supplied a default for the case where you have no
information to fix the adjustable model parameter we cannot recommend any of
the subsequent results. But we do recognise that you may want to use the
asphaltene model for screening purposes and we have developed a procedure to
adjust this parameter based on a knowledge of the reservoir conditions or STO
titration data.
For this example the assumed bubble point is 250K and 70 bar and the reservoir
conditions are 365K and 343 bar. Use the Tools\Matching\Asphaltene Phase to
display the dialogue box, and enter the appropriate values.
214 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
Click on Match and Close: the model parameter values and the amended
petroleum fraction properties will be displayed in the main window. The
asphaltene model has now been defined.
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 215
Click on Plot to display the phase boundary. This will usually show two points
of discontinuity, labelled D. These are the points where the asphaltene
deposition envelope crosses the bubble point line.
These points can be very useful for setting an appropriate starting pressure for
the deposition envelope or providing starting values if these are required. For
this example go back to the Phase Envelope and this time set the phase to
asphaltene, the fraction to zero, the solution type to unspecified and the Initial
value for pressure to 170 bar. Ask for more points to be plotted until the
asphaltene boundary is complete.
216 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
For other examples you may have to plot the upper and lower boundaries
separately. The upper boundary uses the Unspecified solution or Upper
retrograde type solution, the lower boundary the Lower retrograde type of
solution. Alternatively you can try specifying temperature rather than pressure
and/or providing a starting value. We have found asphaltene boundaries most
difficult to plot for very light oils.
If you have a known set of conditions and want to see if, and how much,
asphaltene is present you can use a simple P,T flash. Enter the temperature and
pressure, for example 365K and 170 bar, Click on the P,T icon, or Select the P,T
flash from the Calculate\Standard flash menu. The phases present, and the
composition and amount of each phase, will be reported. Before doing this you
may find it useful to set the units for amounts to mass as this usually reflects the
units of measurement.
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 217
If you want to know the pressure at which asphaltene will start to deposit at any
given temperature then you should use a flash at fixed phase fraction and
temperature. Set the temperature, in this case 350K. Again Click on the icon or
select the calculation option and the dialogue box will appear.
Set the molar phase fraction to zero. To calculate the pressure at which
asphaltene will first appear for pressures above the bubble point, select
Unspecified or Upper retrograde as the solution type and Click on Do Flash.
Multiflash will calculate the pressure on the upper asphaltene phase boundary, in
218 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
this case 227 bar. To obtain the pressure for the lower asphaltene phase
boundary, below the bubble point, follow the same procedure but set the Type of
solution to Lower retrograde. In this case the reported pressure is 104.7 bar.
You can determine the amount of asphaltene flocculation at any set of P,T
conditions using an isothermal flash as described earlier, You may like to get
an idea of the amount of flocculation along any isotherm by carrying out a series
of 4 or 5 calculations.
Set a temperature, e.g. 350K and set the output units to mass fractions. Carry out
a P,T flash at a pressure above and below the deposition envelope. At 275 bar
and 100 bar the asphaltene will be fully dissolved in the oil with a mass fraction
of .012. This is equivalent to the SARA analysis of an asphaltene content of 1.2
mass %. Calculate the pressure for the upper and lower phase boundaries as
before, 228 and 104 bar, at this point the asphaltene is still fully dissolved.
Finally, carry out a bubble point calculation specifying a temperature of 350K
The amount of asphaltene dissolved in the oil is equivalent to 1.02 mass % and
this is the point of maximum deposition. Note the pressure, 132.8 bar. These
points can be plotted as shown below to give either the amount of asphaltene
dissolved in the oil or converted to show the amount deposited.
1.25
1.2
Wt % asphaltene in oil
1.15
1.1
1.05
1
100 120 140 160 180 200 220 240 260
Pressure bar
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 219
The resultant ADE are very close. Inclusion of a n-paraffin distribution will alter
the C6+ molecular weight used to derive one of the model parameters and for
this example this leads to a small reduction in the size of the ADE.
Data Availability
This example of asphaltene flocculation was based on a data set which
comprised the compositional fluid analysis, a SARA analysis, an assumed
bubble point and the reservoir conditions. In this case, as the bubble point was
assumed, the lack of bubble point data has no significant effect on the results.
However, there are other data that may be missing. In all cases the revised
analysis was used to characterise the fluid.
Rematch the bubble point and asphaltene phase at the reservoir conditions as
before and plot the asphaltene deposition envelope (ADE). It is important to
include this step; the matching procedure is cancelled when the fluid is re-
characterised.
220 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
The default procedure estimates both the weight % of asphaltene and the
resin/asphaltene ratio. For this particular example the weight % of asphaltene
with Infoanal2 is very close to the reported value at 1.3 wt% asphaltene
compared to the experimental data of 1.2 wt%. With Infoanal1 the wt% of
asphaltene was underestimated at 0.44 wt% . This results in a difference with
Infoanal1 to both the ADE and the deposition isotherm.
In this case the calculated the ADE are very close to that predicted with a full
SARA analysis whichever analysis method is chosen. This also applies to the
deposition isotherm at 350K.
No reservoir pressure
If you only have the reservoir temperature we have included a facility to estimate
this. Simply enter the bubble point and reservoir temperature as before and
initiate the matching procedure.
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 221
For this particular example the resultant ADE is almost indistinguishable from
the ADE calculated from the real reservoir conditions.
As a corollary to this we have noticed that you usually generate very
conservative ADE when you have a very over-pressured reservoir. If you have a
bubble point measurement at the same temperature as the reservoir temperature
and the reservoir pressure is more than 2.5 times the bubble point a warning
message is generated.
You can continue to match to your reservoir conditions although it may also be
beneficial to generate the model parameters with an estimated reservoir pressure
to see the likely sensitivity.
If, as in our case study, the bubble point is matched at a different temperature to
the reservoir temperature no warning is issued.
222 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
measurement. You simple repeat the procedure but at the Matching/Asphaltene
Phase step you replace the selection of Reservoir conditions with Deposition
envelope. We have assumed a value of 200 bar at 365K
1.25
1.2
Wt % asphaltene in oil
1.1
1.05
1
100 120 140 160 180 200 220 240 260
Pressure bar
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 223
Gas injection
It is known that as gas is injected into a reservoir the likelihood of asphaltene
flocculation is increased. The asphaltene model predicts this trend correctly.
Return to the original ADE, calculated from the asphex.mfl input file with
matched bubble point and reservoir conditions. You can mimic gas injection by
increasing the amount of methane by adding more moles of methane in the drop
down composition box. If you increase the amount of methane from 27.55
moles to 40 moles and replot the ADE you will see that the fluid bubble point
line is at higher pressures and the ADE has expanded.
When looking at the effect of gas injection you should, of course, not rematch
the fluid bubble point or asphaltene phase deposition as doing this will alter the
petroleum fraction properties and model parameters.
You should not use the PVT Analysis GOR option to add the injection gas to the
reservoir fluid. Any re-characterisation cancels the properties and parameters
derived from earlier matching and, as you now have a different fluid, the values
of bubble point and reservoir conditions used for matching are no longer valid.
If you have a complex injection gas and want to study the effect of different gas
injection rates then we suggest the use of an Excel spreadsheet.
Titration
The Infochem asphaltene model was intended for use in predicting the
asphaltene flocculation of live oils and the model parameter generation based on
asphaltene studies of live fluids. However, live oil asphaltene studies can be
expensive, particulalry with the requirement to obtain and transport bootom hole
sales. Some of our users have asked whether titration measurements on dead oils
can be used to generate the model parameters. To date we have only been able
to obtain limited samples of titration data and have traced only one oil, in the
public domain, where there is any information on both asphaltenes in the live oil
and reported titration on the associated stock tank oil (STO), enabling us to
compare results. However, we understand that some of our users have applied
this approach successfully, and for Multiflash 3.3 we have automated the
procedure.
The studies have been limited to titration with heptane.
Our example is based on the titration.mfl file provided. The file includes the live
oil composition and the wt% asphaltene. The reported value was 1.9 wt% for
224 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
the STO, but has been corrected to 1.62 wt% for the live fluid using the method
describe earlier, see Input data on page 211.
Characterise the fluid composition as usual and the return to the main menu,
Tools/Matching/Asphaltene phase. The reported amount of heptane to just cause
asphaltenes to flocculate from the STO at ambient conditions is 1.4 cm3 per g
tank oil. This has been converted to .962 g heptane using the known density.
Enter this value and click on match.
The asphaltene model parameters will be reported in the main window as usual
and the ADE plotted. The resultant ADE is compared to those generated from
matching to a known flocculation point of 54.4 C and 200 bar and to a
combination of reservoir temperature (54.4 C and bubble point (54.4 C and
156.2 bar)
The ADE predicted from matching to titration of the STO is more conservative
than the ADE from flocculation measurements but less conservative than using
reservoir conditions to provide the model parameters. It is believed this has been
the experience for other fluids.
If your titration data does not include the amount of heptane just to initiate
flocculation and it is not possible to deduce this from the other titration results
then the procedure for parameter generation is slightly more complicated and
requires the use of an Excel spreadsheet. In Multiflash for Windows either
characterise the STO, if this composition is provided or flash the characterised
live oil to STO conditions. Using the STO composition match the asphaltene
flocculation to ambient conditions and make a note of the RAE parameter. Save
the problem using the File/Save Problem Setup option. You then need to create
an Excel worksheet to read in this .mfl file. Details of how to do this are
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 225
described in the Excel manual. For our example we have generated the file
STO_titration.mfl
You then need to do two things: add a new component to the list, heptane, and
add the command line describing the asphaltene parameters. This can be copied
from Multiflash for Windows using Tools/Show/Problem However it must be
set up so that the RAP parameter appears in a single cell so that it can be
optimised using the Excel Solver, e.g.
include c:\work directory\exampleoil.mfl";
model MREFASPHALTENE RAEQUIL DATA AAPREEXP
1.00000000 AAEXP 1.00000000 RAPREEXP
0.62542
RAEXP
0.98213 ;
component heptane;
The spreadsheet, titration.xls is then set up to calculate the wt% of asphaltene
deposited for the experimental amounts of heptane added which can then be
compared to the reported wt% asphaltene deposition. This is then used to
optimise the value of RAPREEXP (RAP) using the Excel Tools/Solver.
For our particular example the data reported in the paper included a live oil and a
STO composition, a wt% asphaltene for the STO, which we also corrected to
live oil composition, an asphaltene flocculation point and five points for the
heptane titration.
The reported titration data are plotted below
1.8
1.6
1.4
wt% asphaltene
1.2
0.8 Exptl
0.6
0.4
0.2
0
0 5 10 15 20 25 30 35 40
g C7/g oil
Fitting to the onset flocculation point using the matching facility produced the
following parameters
RAE 0.981265
RAP 0.71881
Whereas fitting to the other four points in Excel gave parameters
RAE 0.98213
RAP 0.68517
These parameters repreent the STO titration data well.
226 Case studies Asphaltene flocculation User Guide for Multiflash for Windows
wt% asphaltene component precipitated as Fn C7 solvent
1.8
1.6
1.4
wt% asphaltene
1.2
1
RAP fit
0.8 Exptl
0.4
0.2
0
0 5 10 15 20 25 30 35 40
g C7/g oil
The ADE predicted using model parameters generated this way is more
conservative than the ADE generated using onset titration data, which is in turn
more conservative than that generated from flocculation data.
It is clearly preferrable to generate the live oil ADE from live oil data. Some
predictions are possible from titration data but is is important that all data are
compatible, particularly the compositions of the STO and the flashed liquid.
User Guide for Multiflash for Windows Case studies Asphaltene flocculation 227
Case studies Combined solids
Introduction
The previous three case studies looked at solid formation for hydrates, waxes
and asphaltenes as separate problems. However, for some fluids at certain
conditions it is possible that any or all of these may form at the same time. The
formation of any one will affect the overall composition of the fluid and may
therefore affect the formation of the other solidsTo examine this possibility we
have included a Combined Solids model option. The particular model options
for each solid have been chosen to provide the best Infochem can offer whilst
ensuring compatibility. The common fluid phase model is RKSA. The hydrate
models therefore use RKSAINFO as the fluid model, combined with the
Electrolyte salt model. The wax model is Coutinho and there is only one
asphaltene model. The Combined Solids option is only designed to look at solid
formation, if you want to study the more complex problems such as hydrate
inhibition you should still choose the dedicated Hydrates model set. In fact, you
will see messages to this effect if you only choose a single solid phase in the
Combined Solids option.
Asphaltene flocculation
To understand what happens when more than one solid forms a useful starting
point is to examine asphaltene flocculation alone. The example input file
provided is combsolid.mfl. This includes an oil composition to C20+ which has
a molecular weight of 81, wt% resin of 12.04 and wt% asphaltene of 0.7. The
fluid is characterised from C6 with 15 fractions. The resins and asphaltenes are
allocated as shown below:
25R R67-75 .692746
26R R75+ .516726
27AS ASPHALTENE .700000
The asphaltene model parameters are matched with a bubble point of 120F and
2650 psia and an asphaltene flocculation point of 120F and 8750 psia. The
predicted ADE is plotted below.
User Guide for Multiflash for Windows Case studies Combined solids 229
Wax and Asphaltene precipitation
To see the effect of simultaneous wax and asphaltene precipitation we first need
to re-characterise the fluid with a n-paraffin distribution in order to apply the
Coutinho model. In the PVT form tick the bos to estimate wax content as none
is known. The n-paraffin distribution is also set to C6 and 15 fractions.
The separation of the n-paraffins from the remainder of the liquid also alters the
distribution and properties of the resins and asphaltenes:
19RI R33-37 1.90353
20RI R37-42 2.53946
21RI R42-47 2.26335
22RI R47-54 1.96595
23RI R54-63 1.66832
24RI R63-74 1.16583
25RI R74 1.682065E-02
26RI R75+ .516726
27AI ASPHALTENE .700000
This in itself will alter the resin/asphaltene interaction. Allowing the wax to
form will then remove some of the n-paraffins from the fluid again changing the
proportion of resins in the remaining fluid.
To see the effect choose the Combined Solids option from Select/Model set and
specify wax and asphaltenes as the solid phases. Eliminate Hydrates, water and
ice for the time being.
230 Case studies Combined solids User Guide for Multiflash for Windows
As the model has been re-defined we will need to match the asphaltene
parameters again, using the same input data. The new parameters will be
slightly different because of the altered distribution.
Now plot the gas and asphaltene boundaries as before then add the wax
boundary.
As you can see changing the resin distribution and removing some of the n-
paraffins has the effect of stabilising the asphaltene and thus lowering the upper
ADE once wax has formed.
User Guide for Multiflash for Windows Case studies Combined solids 231
As we have chosen to re-define the model we also need to re-match the
asphaltene parameters. This is best done in the absence of water, which is why
the initial water composition was set to zero. Using the same input data the
asphaltene parameters will be exactly the same as for the wax and asphaltene
study.
Now add the water composition, 10g. Adding too much water may cause
difficulties when plotting the ADE.
With water present use the phase envelope plotter to generate all the phase
boundaries. Starting point for the asphaltene bounday may have to be changed
as it is affected by the presence of the other solids.
The wax boundary is not affected by the addition of water or the formation of
hydrate, which occurs at lower temperatures. However, the effect on the upper
ADE is significant. As the hydrate is formed the light gas hydrate formers are
removed from the fluid. This is in effect the reverse of gas injection and the
asphaltene is stabilised with flocculation occuring at lower temperatures.
Of course with water present there is also the possiblity of a separate water phase
232 Case studies Combined solids User Guide for Multiflash for Windows
If the fluid is flashed at 70F and 1750 psia Multiflash will predict the formation
of 6 phases; gas, hydrocarbon liquid, water, hydrate, aspahltene and wax. With
only 10g of water present reducing the temperature slightly removes the water
phase owing to the formation of additional hydrate.
Of course, in practice the formation of some many phases will be affected by
kinetics as well as thermodynamics.
User Guide for Multiflash for Windows Case studies Combined solids 233
Case studies Excel
spreadsheets
Introduction
Although only accessible if you have licensed the Excel add-in option there are
some problems which are best approached using Excel. Some of these are
discussed in the Multiflash Excel manual, such as generating tables of pure
component data or using linked flashes or recycles for simple flowsheet
calculations.
Those presented here were set up following user requests and include generating
binary interaction parameters for activity coefficient models and linking
predictions of solid formation to a common fluid analysis.
Although we have not included them here some users wish to fit their own
experimental data for components not included in their version of Multiflash. To
help users to do this we do have available a series of spreadsheets for the fitting
of pure component data. They are not issued with the standard installation but
we will supply them on request.
UNFACFIT.xls
UNIFAC is a very useful model as the binary interaction parameters are
generated from the group structures of the pure components and so reasonable
predictions of phase equilibria can be obtained for polar systems without the
need for stored BIPs.
However, there may be times when you wish to use an alternative model such as
NRTL. Although we are continually expanding our BIP databank there may be
some binary pairs in your mixture for which we do not have stored NRTL
parameters. If you do not have the time to search for experimental data for the
missing pairs, or are unable to find any, then this spreadsheet allows you to
generate the phase equilibria data from UNIFAC, providing group structures are
available for your chosen components, and then fit this data using another
activity model.
The spreadsheet has several worksheets.
Notes
The first spreadsheet consists of notes on how to use UNFICAFIT.xls and how
to enter the fitted BIPs in Multiflash.
User Guide for Multiflash for Windows Case studies Excel spreadsheets 235
UNIFAC
This is the worksheet where you generate the phase equilibria data (liquid and
gas phase compositions and temperature or pressure) that you are going to fit.
You specify, by entering information in the appropriate cell:
The databank to act as the source of pure component data, either
Infodata or DIPPR
The names of the two components for your binary pair
Whether you wish to generate data for an isotherm or isobar and
your chosen temperature or pressure
The required data is then generated, including column headings and plots. The
composition range is fixed and the units are SI. There is no need to change these
although it is possible.
An Error box reports the status of the data generation. This should be OK if the
UNIFAC group structures are available for your chosen components. An error
status of 13201 would indicate that the structures are missing for one or both
compounds.
Once the data has been generated you can move to the worksheet for the model
you wish to use, WilsonE, UNIQUAC VLE or NRTL VLE.
236 Case studies Excel spreadsheets User Guide for Multiflash for Windows
VLEFIT.xls
This is substantially the same as UNIFACFIT.xls but the starting point is
experimental data rather than data generated from the UNIFAC model.
Instead of the first UNIFAC worksheet there is an Experimental worksheet to
enter the data. Again you can choose the data source for your pure component
data and indicate whether your chosen data is along an isotherm or isobar. In
order to minimise effort this spreadsheet does allow you to choose the units for
temperature and pressure to match those measured. The temperature or pressure
for the isotherm or isobar should be entered as should the values for x, y and
associated T or P.
We have chosen a limited array for data entry. If you have more data and are
familiar with Excel you can extend the range although you will need to
remember to change the cell references in the dependent worksheets. Otherwise
you should limit the data by choosing suitable sets from the data available.
If you have less data then you should enter #N/A in the cells which would
otherwise be empty or retain values for earlier entries. This is necessary for the
Excel Solver to operate correctly. For some data sets you may have P,x or T,x
but no data for gas composition, y. In this case it is better to enter #N/A for the y
compositions. If you fail to do this the Solver will still function provided the
minimisation criteria is based on difference in temperature or pressure the
default. However, the plots for x,y will not be relevant and should be ignored.
As with UNIFACFIT.xls you can fit the experimental data to generate BIPs for
WilsonE, UNIQUAC VLE or NRTL VLE by choosing the appropriate
worksheet.
User Guide for Multiflash for Windows Case studies Excel spreadsheets 237
PVT Analysis
This work sheet characterises the fluid according to the fluid composition
provided. In common with our other spreadsheets input data are marked in red.
The list of possible components is based on the default component list used in
our PVT Analysis utility. The user enters the compositions and any other
information available such as the molecular weight and specific gravity. The
SARA analysis can be entered; the resin and asphaltene amounts are needed for
the asphaltene model although they can be estimated if required. The user can
specify the starting point and the number of fractions for the characterisation
although we would recommend staying with C6 and 15 fractions. The units for
calculation are also set in this worksheet.
Once the characterisation has been carried out a bubble point is predicted using
this characterisation at a temperature or pressure set by the user. This allows the
user to decide whether to tune the petroleum fraction properties to match a
known bubble point or if this is unnecessary.
238 Case studies Excel spreadsheets User Guide for Multiflash for Windows
Wax
The next worksheet is dedicated to prediction of wax formation, although the
worksheets for wax, asphaltene and hydrates are not inter-dependent and can be
used in any order.
The user can choose to use the fluid characterisation direct from the PVT
Analysis or with petroleum fraction properties tuned to match a bubble point.
The first set of calculations predict the wax appearance temperature (WAT)
without any further tuning plus the amount of wax formed at a user specified
T,P. The WAT is plotted automatically as a function of pressure. The starting
pressure and step can set by the user to obtain the pressure range of choice.
These calculations are repeated based on matching to a known WAT.
User Guide for Multiflash for Windows Case studies Excel spreadsheets 239
Asphaltenes
The asphaltene worksheet again offers the choice of using the PVT Analysis
characterisation direct or the characterisation after matching to a known bubble
point. For asphaltene modelling we would recommend the latter.
The options for producing the asphaltene model parameters are not as flexible in
Excel as in the Windows front end. You are limited to two options, the
flocculation or reservoir conditions and you must supply both temperature and
pressure.
After matching the user can set either temperature or pressure and calculate the
corresponding P or T for the upper and lower boundaries of the flocculation
envelope. There is also an option for entering a set of T,P and calculating the
amount of asphaltene formed at those conditions.
Every effort has been made to plot the asphaltene flocculation envelope
automatically with starting points derived from the flocculation or reservoir
conditions. However, as the engineers using our Windows phase envelope
facility will appreciate it is difficult to make this absolutely foolproof.
240 Case studies Excel spreadsheets User Guide for Multiflash for Windows
Hydrates
The hydrate functionality is well served in our Windows software and easily
used. We have only added a hydrate worksheet here for completeness and to
allow the engineer to carry out quick checks for possible hydrate formation. It
encapsulates the main features of our hydrate model but does not have the
flexibility of the Windows program.
The model used in solids.xls is based on RKSA (Infochem) as the fluid phase
model, in solids31.xls the model is based on CPA and the new salt model.
The user needs to add an amount of water to the fluid and this can either be pure
water or produced water with the salt content defined by ion analysis or total
dissolved solid. The hydrate dissociation temperature can be calculated at a
single pressure or plotted as a function of pressure. The hydrate is defined as
hydrate2 only, which is the usual hydrate formed especially as the spreadsheet is
designed to work with oils rather than natural gases.
There is also a section in the worksheet for looking at the use of inhibitors.
These are limited to the two most common, methanol or MEG. They can be
added in fixed amount or the concentration required for hydrate inhibition at set
conditions can be predicted.
User Guide for Multiflash for Windows Case studies Excel spreadsheets 241
Users who want to investigate hydrate behaviour only may find the
hydrateinfo.xls and hydratecpa.xls spreadsheets useful. These have a restricted
component list (gases and gas condensates) but offer a choice of fluid and salt
model and a wider choice of caclulations.
242 Case studies Excel spreadsheets User Guide for Multiflash for Windows
Case studies - chemical
equilibria
Introduction
Most thermodynamic simulation in process engineering centres on the need to
calculate phase equilibria for separation processes, especially distillation.
However chemical equilibria is another area where thermodynamic information
can be exploited to make predictions about chemical processes.
The chemical reaction module in Multiflash is a utility for performing
simultaneous phase and chemical equilibrium calculations. It can handle
equilibria involving combinations of one gas phase, one liquid phase and any
number of pure solids.
The chemical reaction module does not rely on reaction schemes. You do not
need to specify any reaction mechanism but only list all the possible products
and reactants.
The applications are many and varied but a sample is discussed here
Xylene isomerisation
To start with a very simple example, select ortho-, meta- and para-xylene from
the INFODATA fluids bank.
Select RKS using the route Select/Model set/Equations of State/RKS. The
model set will be used to predict the phase properties and any of the cubic
equation of state models would be acceptable for this case study.
Enter a temperature of 575K and a pressure of 10 bar (remember to set the
pressure and temperature units correctly).
User Guide for Multiflash for Windows Case studies - chemical equilibria 243
At the same conditions the ratios of the three xylenes will remain the same.
If you reduce the temperature to 300K and the pressure to 1 bar the mixture will
be in the liquid phase. The equilibrium concentrations of the three xylenes are
slightly, but not significantly, different and again are unaffected by the input
compositions
244 Case studies - chemical equilibria User Guide for Multiflash for Windows
Click on the chemical reaction button,
Under these conditions 4.96 moles of hydrogen, 1.974 moles of carbon
monoxide and 0.00668 moles of carbon dioxide are produced.
Vary the ratio of water to ethane and note the increase in the amounts of carbon
dioxide as the ratio increases.
You can look at the enthalpy changes for the reactions by carrying out a simple
P,T flash to obtain the enthalpy of the reactants and the chemical P,T reaction
flash to see the enthalpy of the products.
User Guide for Multiflash for Windows Case studies - chemical equilibria 245
Appendix - Multiflash
Commands
Introduction
The Multiflash command language is common to all Multiflash implementations
- DOS, Excel, VB etc. A complete list of all commands and information on how
to use them is contained in the Multiflash Command Reference manual.
In the Windows version the use of commands has largely been replaced by
menus and icons. However, not all the facilities available in the command
processor version of Multiflash have been incorporated as menu options in the
current version of Multiflash for Windows. An example might be reverting to a
previous version of the Infochem BIP databank to maintain backward
compatibility. To allow you full access to all Multiflash facilities a Tools
command option is available, see Tools on page 35, which allows you to enter
a command and apply this in the Windows version.
Commands are also used to specify problems in problem setup files. If the set
up file is created by saving a problem specified interactively then the appropriate
commands will be transferred automatically to the set up file.
Defining models
The standard thermodynamic and transport property models available in
Multiflash are specified in the model sets and model configuration files supplied.
However, you may wish to set up your own model definition, for example you
may wish to use an activity style mixing rule with an equation of state model.
You may also wish to group together different models to describe different
User Guide for Multiflash for Windows Appendix - Multiflash Commands 247
properties, such as using an equation of state to describe the properties of a
refrigerant mixture but defining the density in terms of ideal mixing.
In general the MODELS command defines a thermodynamic or transport
property model for mixtures. The command has the format:
MODEL model_id MF_model_name [Model_options]
where
1. model_id is a user-defined name that will be used to refer to the
particular combination of the property model and options specified.
2. MF_model_name is the Multiflash name for the basic model. The
list of recognised models is given below together with the
applicable options.
3. Model_options are additional keywords that describe model
variants, references to other, previously-defined, models or
references to the source of binary interaction parameters.
Any .mfc file will provide an example of how to set up a model definition.
248 Appendix - Multiflash Commands User Guide for Multiflash for Windows
A phase descriptor (PD) contains all the information required to identify a phase
and to retrieve its thermodynamic properties. A PD must be specified for each
possible phase that Multiflash is to consider. The PD command is used to define
a phase descriptor (PD). To exclude the formation of a particular phase type, e.g.
gas, the corresponding PD should be omitted or erased. The command has the
format:
PD pd_id phase_type model_identifiers
or
PD pd_id erase
The following table gives the valid options and settings:
User Guide for Multiflash for Windows Appendix - Multiflash Commands 249
command description notes
parameter
pd_id user-defined name that will any unique alphanumeric
be used to refer to the string, e.g. liquid1
particular instance of phase
type and associated models
phase_type a keyword that defines the 1. gas, vapor and vapour are
phase type, valid settings are: synonyms.
condensed 2. condensed means a pure
gas solid phase.
hydrate 3. solidsolution means a
liquid mixed solid phase
solidsolution
vapor
vapour
model_identifiers identifiers for up to six 1. the model identifiers are
models that will be used to the user-defined names
evaluate the thermodynamic associated with the models
and transport properties of (see description of
the phase. Models for the MODELS command)
following properties may be 2. at least one
specified in the order given: thermodynamic model must
1. fugacity (K-values) be defined (the same model
2. volume/density (optional) is then used for all
3. enthalpy/entropy thermodynamic properties)
(optional) 3. transport property models
4. viscosity (optional) need only be defined if
5. thermal conductivity output of these properties is
(optional) required
6. surface tension (optional)
erase erases (removes) the PD 1. the pd_id must have been
from the list of PDs available previously defined
for Multiflash 2. all information associated
with the PD is lost
The standard model sets and model configuration files include four phase
descriptors for GAS, LIQUID1, LIQUID2 and WATER. If you use the
Select/Freeze-out components option to apply the freeze-out model, see The
Freeze-out model on page 70, a phase descriptor will be automatically
generated from the component name. However, you can change this name using
the phase descriptor command.
You may wish to erase a phase descriptor to limit the number of phases
considered when solving a flash calculation, see Troubleshooting - flash
calculations on page 147.
The KEY command is used to define a key component for a PD. A key
component helps to identify a particular phase when two or more PDs would
otherwise be indistinguishable. It is not necessary to define a key component
unless a flash calculation needs to identify phases uniquely (e.g. a search for a
particular phase fraction). The command has the format:
KEY pd_id key_component_id
or:
KEY pd_id not key_component_id
250 Appendix - Multiflash Commands User Guide for Multiflash for Windows
component name is preceded by the keyword not , this means that the
component should be present in the minimum relative concentration.
The model sets and model configuration files supplied identify one liquid phase
as having water as the key component and the other two liquid phases in terms of
not being the water phase. There may be a case where you would wish to
allocate a key component to one of these, e.g.
Key liquid2 CO2;
or
Key liquid1 heaviest
User Guide for Multiflash for Windows Appendix - Multiflash Commands 251
C
Calculate 25
Calculating asphaltene flocculation conditions 215
Calculating the bubble point curve 164
Table 26
V
Tables 10
Tabular output 115, 147 Vapour-liquid-liquid equilibria 183
Excel interface 115 Viewing and editing pure component data. 69
PSF file for HTFS programs 147 Viscosity 42, 106
PVT file for PIPESIM 147 Matching liquid viscosity 106
Technical support 154 Models 42
W
Warnings 142, 144, 183, 243
Additional phases 183
Chemical reaction 243
Convergence 142
Water cut 96
Wax 41, 49, 105, 205, 239
Case study 205
Coutinho Model 41
Defining Wax model 49
Matching WAT 105
Multisolid Model 41
Wax and Asphaltene precipitation 230
Wax Content 95
Website support 154
What is a model? 29
What the model definition means 46
What types of model are available? 29
When to use activity coefficient models 36
When to use cubic equations of state 31
When to use equation of state methods 30
When you may need to use commands 247
Will hydrates form at given P and T ? 192
Wilson A equation 35
Wilson A equation, 35
Wilson A model 35
Wilson E equation 35
Wilson E model 35
Write to Excel 130
Writing the results to a file 140
X
Xylene isomerisation 243