User Guide for

Multiflash for Windows

Infochem/KBC Process Technology Ltd

Version 6.0

March 2015

Infochem/KBC Process Technology Ltd

93 Great Suffolk Street
London SE1 0BX
Tel: +44 20 7357 0800
e-mail: [email protected]
This User Guide and the information contained within is the copyright of KBC Advanced Technologies plc
© 2015.
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 KBC Advanced Technologies plc 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
Contents iii

Introduction
Introduction to Multiflash 3
The Multiflash user interface 3
Results output 5
Phase labelling 6
Flash calculations available in Multiflash 7
Bubble and dew point flash calculations 8
Model files 9
Specifying a model 9
Configuring Multiflash 11
Specifying default units 11
Specifying units during a session 12
Specifying folder locations 13

Using Multiflash
Defining fluids 17
Defining a standard fluid 17
Defining a petroleum fraction 18
Editing petroleum fraction data 20
Viewing pure component properties 20
Editing pure component properties 22
Editing temperature-dependent properties 23
Defining a fluid using a PVT analysis 24
Defining a fluid using a black oil analysis 27
Defining a fluid from distillation data 29
Adding a user-defined component 31
Applying the freeze-out model 33
Blending fluids 34
Blending example: petroleum fluids 35
Blending example: asphaltenic crudes 38
Blending example: waxy crudes 42
Exploring the effect of user-defined pseudocomponents 46
Characterizing multiple fluids 49
Using mud numerical cleaning 52
Using the delumping tool 54
Basic flash calculations 56
Performing single flash calculations 57
Calculating bubble and dew points 58
Other preconfigured calculations 58
Performing a fixed phase flash calculation 59
Using the tolerance calculation tool 61
Calculating pure component properties 63
The phase envelope plotter 65
Plotting phase boundaries 65
Scaling the phase plot 68
Using initial values for the phase plotter 68
Plotting property boundaries 69
Generating other plot types 71

User Guide for Multiflash for Windows Contents • iii

 Exporting phase plot data 72
Working with hydrates 74
Specifying the hydrate model 74
Calculating hydrate formation at a given pressure and temperature 76
Calculating hydrate formation and dissociation 79
Determining maximum allowable water content 85
Adding inhibitors with the inhibitor calculator 88
Salt calculator 90
Calculating inhibitor amounts required to suppress hydrate formation 92
Looking at the effect of inhibitors 94
Scale precipitation 98
Working with asphaltenes 103
Preparing for asphaltene calculations 103
Water and asphaltene calculations 104
Specifying the asphaltene model 105
Tuning the asphaltene model 106
Looking at the effect of input data on the asphaltene model 108
Looking at the effect of n-paraffins on the asphaltene model 114
Calculating asphaltene precipitation conditions 117
Calculations with no asphaltene precipitation data 119
Looking at the effect of gas injection 122
Working with waxes 125
Specifying the wax model 125
Tuning the wax model 127
Calculating the wax appearance temperature 129
Calculating wax precipitation 131
Plotting the wax phase envelope 132
Working with mixed solids 136
Looking at the effect of multiple solids formation 136
Calculate the APE with a wax phase present 138
Calculate the APE with hydrates and a wax phase present 141
Working with mercury species 144
Distribution of mercury species 144
Specifying the mercury model 144
Calculating mercury partitioning and dropout 145
Working with binary interaction parameters 152
Viewing binary interaction parameter values 152
Editing binary interaction parameter values 154
Looking at the effect of binary interaction parameters 154
Model tuning with PVT lab tests 157
Entering PVT lab test data 158
Validating data using the PVT lab tests 160
Simulating an experiment using the PVT lab tests 162
Tuning a model using the PVT lab tests 164
Working with polar systems 168
Comparing the polar models 168
Exploring liquid-liquid equilibria 169
Identifying azeotropes 170
Identifying a eutectic point 172
Exchanging data with other programs 174
Exporting PIPESIM PVT files 174
Exporting OLGA files 176
Exporting PROSPER PVT files 178
Exporting a CAPE-OPEN property package 180
Exporting a Multiflash legacy file 180
Importing PVTsim files 180
UNIFACFIT.xls 181

iv • Contents User Guide for Multiflash for Windows

 Using the spreadsheet 182
VLEFIT.xls 183
Using the spreadsheet 183

Multiflash Reference
Phases and components 187
Phase diagram: A brief description 187
Phase descriptors and key components 188
Key components 189
Components 190
Component properties 190
Enthalpy and entropy definition 193
Activity model enthalpy 194
Multiflash models 196
Models and component data requirements 196
Tuning models 199
Equation of state models 201
Equations of state available in Multiflash 201
Differences between the PR model in Multiflash and Aspen Hysys 205
Advanced equation of state options 206
The Peneloux density correction 206
Fitting the vapour pressure curve 206
Mixing rules 206
CSMA and GERG-2008 reference fluids 206
Activity coefficient models 208
Liquid activity coefficient models available in Multiflash 208
Solid phase models 210
Solid freeze-out model 210
Scaling 210
Hydrate formation and inhibition models 210
Hydrate model 210
Nucleation model 212
Ice modelling 213
Inhibitor modelling 213
Phases for hydrate modelling 213
Wax precipitation model 214
Asphaltene flocculation model 215
Combined solids model 215
Transport property models 216
Viscosity 216
Thermal conductivity 217
Surface tension 218
Diffusion coefficient 219
Binary interaction parameters 220
Temperature dependence 220
Units 220
BIPs and models 221
BIPs for CSMA and GERG mixing rule 221
BIPs available in Multiflash 222
Petroleum fluids 223
PVT laboratory analysis 223
True boiling point distillation data 223
D86 distillation data 223
Characterization 224
Data validation in PVT experiments 224

User Guide for Multiflash for Windows Contents • v

 Constant-mass expansion 224
Differential liberation 225
Constant-volume depletion 225
Separator test 225
How the blending method works 226
Differences between blending and characterizing multiple fluids 226
Troubleshooting 227
Models 227
Input conditions 228
BIPs 228
PVT analysis 228
Matching properties 229
Flash calculations 229
Components 231
Errors and warning messages 232
Technical support 232
About Multiflash 232

Glossary
Glossary 235

Index
Index 239

vi • Contents User Guide for Multiflash for Windows

Introduction to Multiflash
Multiflash is a powerful and versatile system for modelling physical properties and phase equilibria. It
can be used as a stand-alone program or in conjunction with other software.
Multiflash can provide:

All the thermodynamic and transport properties needed for engineering studies.
Comprehensive fluid characterisation and model tuning for petroleum fluids.
Flash calculations to determine the phases present at specified conditions and their type, com-
position and amounts.
Complete phase envelopes, showing phase boundaries and critical points.
Modelling solids formation, including pure solids, halide scales, hydrates, waxes and asphaltenes.

Multiflash has a comprehensive set of configurable options, making it easy to specify all aspects of a
study. Each configuration can be saved for future use with Multiflash or other compatible applications.
Multiflash can be accessed using:

A graphical user interface.

An add-in for Microsoft Excel.
An interface for use with any application that is CAPE-OPEN enabled.
Any software that can call a Windows DLL. We provide support for applications written in vari-
ous programming languages, including C++, Visual Basic and Fortran. Linux applications can
also be supported.

Separate documentation is available for each of these interfaces.

The Multiflash user interface

The Multiflash user interface has the main areas shown in the screenshot.

User Guide for Multiflash for Windows Introduction to Multiflash • 3

 Item Description

1 The ribbon provides access to all functions available through the user interface. Related
functions are grouped on each ribbon.

2 Each tab contains a separate Multiflash problem. The current tab is the one on which all
functions are performed.

3 The Fluid composition panel shows the name and amount of each component that
comprises the fluid under investigation. You must enter a fluid composition before any
calculation can be made. You can edit the amount of a component at any time by clicking
on the value and then typing the new amount in the units specified in the column header.

4 The Calculations history panel shows each calculation performed on the fluid. If you click
on any calculation, the results of that calculation appear in the Results area.

5 The Log panel shows warning and error messages, labelled with a time stamp and the calcu-
lation used.
If, at any time, your calculation fails, use the messages shown here to help you diagnose the
problem with your calculation.
You can clear the error messages by right-clicking within the Log panel, and selecting
Clear Errors.

6 The Fluid identification panel is for adding comments and notes. This can be useful for
future reference, for example, to identify the study and the source of the fluid data. Any text
that you enter is saved as part of the .mfl file and shown when the file is reloaded.

7 The Conditions panel is where you specify the initial conditions for Multiflash calcu-
lations. The conditions required depend on the calculation. Only the conditions required for
your chosen calculation are used, so you can have values for other conditions, foe example,
if you are going to perform a series of different flash calculations. You can specify the units
used for input and output values.

4 • Introduction to Multiflash User Guide for Multiflash for Windows

 Item Description

8 The Results area shows all the values generated by the most recent Multiflash calculation.
These generally consist of a summary together with the phase fractions, composition and
properties, see Results output.
If you right-click in any of the tables, you can copy the data and paste it into other applic-
ations, for example, Microsoft Excel.

You can rearrange or combine the panels (2-7) into tabbed groups by holding down the left mouse
button on the panel title bar and dragging to your preferred location. Valid locations are identified by a
colour change or rectangular outline on the background of the main Multiflash window, depending on
your current style setting. Your changes are valid only for the current session.

Results output
The results of every calculation are displayed in the Results area. The output will vary slightly, depend-
ing on the type of calculation and the level of physical property output specified, but will be in the style
shown in the screenshot.
Tip: If, at any time, your calculation fails, use the messages shown in the Log panel to help you
diagnose the problem with your calculation.

The Results area provides the information shown in the following table.

Item Description

Temperature The temperature of your calculated result.

User Guide for Multiflash for Windows Introduction to Multiflash • 5

Defining fluids
In Multiflash, a fluid is the mixture of components on which you carry out calculations. The definition of
your fluid is therefore critical to the successful use of Multiflash.
A fluid can be defined in several ways:

As a mixture of standard components.

As a set of petroleum fractions.
As a mixture of standard components and petroleum fractions.
As a petroleum fluid characterised by a comprehensive PVT laboratory analysis.
As a petroleum fluid characterised from limited data (black oil analysis).
As a petroleum fluid characterised from experimental distillation data.
As a blend of previously characterised petroleum fluids.

Defining a standard fluid

A standard fluid comprises standard components available in Multiflash. You can specify a maximum of
200 components in a standard fluid.
You can add or remove components from your fluid at any time. One reason for doing so would be to
add water or another component for a tolerance or saturation calculation.
To define a standard fluid:

1. On the Home ribbon, click Components.

User Guide for Multiflash for Windows Defining fluids • 17

 2. Select the databank from which you want to take component properties.
3. If required, filter the component list as shown in the table.

To filter Do this
by

Name Select Component name/synonym, and start entering the name above the compon-
ent list.
The text that you enter is interpreted as a substring filter, so the component list
contains only those names that contain the text string that you enter.
Tip: If you want to see all synonyms of the components in the list, check Show
component synonyms.

Chemical Select Formula, enter the chemical formula, for example, C6H14, and then click
formula Search. You must use upper case letters for the elements. You can use the asterisk
(*) to represent any number for an element.
Your search formula must include the letter of each element in the component. For
example, C*H*O* finds only components that contain carbon, hydrogen and
oxygen; it will not find any ethanolamines, because they contain nitrogen.

4. Scroll through the list and click on the components that you want to add.
Tip: You can select multiple components by holding down the Ctrl key while you make selec-
tions. Contiguous selections can be made by clicking the first component, and then holding down
the Shift key while you click the component at the end of a set.
5. Click Add selected components.
Result: The selected components appear in the Currently selected components list.
6. If required, you can also add a user-defined component or petroleum fraction.
7. If you need to remove one or more components, select them in the Currently selected com-
ponents list, and then click Delete selected components.
8. Click OK.
9. In the Multiflash window, specify the amounts of each component, by clicking in the Amount
column, and entering the required amount.
Tip: To enter mole fractions or mass fractions, select an appropriate unit to use, and then enter
values that sum to one.

Result: Your fluid is fully defined and ready for calculations.

Defining a petroleum fraction

You might have data about petroleum fractions in your fluid; for example, data from other process simu-
lation software. If so, you can create a petroleum fraction using that data. You can specify a maximum of
100 petroleum fractions.

18 • Defining fluids User Guide for Multiflash for Windows

Basic flash calculations
In a flash calculation the overall composition and any two of the following variables are fixed:

Temperature (T)
Pressure (P)
Volume (V)
Enthalpy (H)
Entropy (S)
Internal energy (U)
Amount of a phase

The flash calculation enables you to determine, subject to the constraints imposed (the two fixed quant-
ities), the number and type of phases present and the composition and properties of those phases. This is
based on the thermodynamic principles that at equilibrium:

The fugacities of each component in all phases are equal.

The temperature of all phases is the same.
The pressure of all phases is the same.

The calculations available in Multiflash can be divided into these categories:

Single flash calculations, where any two quantities, excluding phase amount, are specified, and
the amounts and compositions of all phases at equilibrium are calculated.
Fixed phase calculations, where one of the fixed quantities is the amount of one phase. Bubble
and dew point calculations, where the first gas or liquid appears at a fixed temperature or pressure,
are a special case of these calculations, where the gas phase (for bubble point) or liquid phase (for
dew point) is set to 0.
Phase envelope or sequential flash calculations to follow a phase boundary or to simulate a labor-
atory procedure.

Tip: If you need to carry out many single calculations and generate tabular output, use the Multiflash
Excel interface. See the separate document Multiflash Excel Interface User Guide for details.
The general approach to a Multiflash calculation is as follows:

1. Define the fluid by specifying the components and their amount.

2. Specify the model to use, including the required phases.
3. If required, change the units of measurement for the calculation.
4. Specify any input conditions required for the calculation.
5. Perform the calculation.

56 • Basic flash calculations User Guide for Multiflash for Windows

Working with hydrates
Note: You can only perform hydrate calculations if your Multiflash licence includes the hydrates option.
Natural gas hydrates are solid, ice-like compounds of water and the light components of natural gas.
Some heavier hydrocarbons found in gas condensates and oils are also known to form hydrates if smaller
molecules, such as methane or nitrogen, are present to stabilise the structure. Hydrates can form at temper-
atures 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; up to seven phases must be
considered, even without considering the possibility of scale formation. The behaviour is particularly
complex if there is significant mutual solubility between phases, for example, when inhibitors or CO2 are
present.
Multiflash offers a powerful set of thermodynamic models and calculation techniques for modelling
hydrates. In principle, hydrate calculations with Multiflash are no different from flash calculations for
fluid phases alone. Multiflash treats fluid and solid phases on the same basis and the full range of flashes
can be carried out for fluids with hydrates. The models used in Multiflash hydrate calculations are
described briefly in the reference section of this help file. For a more detailed description, refer to the
Models and Physical Properties User Guide.
In addition to applying all the available flash calculations to a hydrate system, Multiflash enables you to
perform the following types of hydrate calculation:

Prediction of hydrate formation at a specific temperature and pressure.

Hydrate formation and dissociation temperature at a given pressure.
Hydrate formation and dissociation pressure at a given temperature.
Hydrate phase boundaries for formation and dissociation.
Minimum water content for hydrate formation.
The effect of inhibitors, including salt inhibition, on hydrate formation and dissociation.
Dosage calculations of the amount of inhibitor required to suppress hydrate formation under spe-
cified conditions.
Prediction of scale precipitation.

Requirement: You must include water explicitly in your fluid to perform hydrate calculations. The
amount of water may influence the results of the calculations, particularly when inhibitors or water-
soluble gases are present or the fluid is under-saturated with water.

Specifying the hydrate model

To ensure that reliable results are obtained for hydrate calculations, you must specify the hydrate model
appropriately for the problem you are trying to solve.
For many basic types of hydrate calculation, you do not need to specify the model manually. Instead, you
can use the preconfigured model setups, available from the Hydrates ribbon:

74 • Working with hydrates User Guide for Multiflash for Windows

 Model setup Use for

These calculations with no salts present:

Standard flash calculations

Hydrate dissociation
Hydrate structure types I and II only
Hydrate inhibition

These calculations with salts present:

Standard flash calculations

Hydrate dissociation
Hydrate structure types I and II only
Hydrate inhibition

If you want to perform other types of calculation, or change the transport property models, you must
specify the model manually.
To specify the hydrate model for other calculation types:

1. On the Models ribbon, select .

2. From the model list, select Hydrates.

The image shows the default settings for the hydrates model.
3. Choose the model and phases required for your particular calculation, as shown in the following
table.

Calculation type Model Additional non-default

phase required‡

Some components form structure CPA-Infochem Hydrate H

H hydrates (no salts present).

User Guide for Multiflash for Windows Working with hydrates • 75

 Calculation type Model Additional non-default
phase required‡

Hydrate formation (no salts CPA-Infochem Phase Nucleation

present)

Some components form structure CPA-Infochem + electrolyte Hydrate H

H hydrates (salts present).

Hydrate formation (salts present) CPA-Infochem + electrolyte Phase Nucleation

Salt precipitation CPA-Infochem + electrolyte Halide Scales

(scale formation)
‡Required phases are additive. For example, if you want to calculate formation of structure H hydrates, you should select
the additional phases for both calculation types, Hydrate H and Phase Nucleation.

4. If required, choose an alternative model for your transport properties.

5. Click Define Model.
6. On the success message, click OK.

Calculating hydrate formation at a given pressure

and temperature
Problem:
Will hydrates form at a given temperature and pressure?
Approach:

1. Define your fluid.

2. Specify the hydrate model.
3. Perform a PT flash calculation at your required temperature and pressure, and check the results for
the presence of a hydrate phase.

For the following example, you can use the file hydrate.mfl, which describes a gas condensate, if you do
not want to enter the model and component data manually.
Try it yourself:

1. If you are using our example file, on the File menu, click Open, open the file hydrate.mfl, and
then proceed to step 7.
Tip: By default, the example files are in the MFL Files folder of the Multiflash installation.
2. On the Home ribbon, click Units, ensure that the input and output pressure units are MPa, the
input and output temperature units are K, the amount input units are mol, and the amount output
units are g, and then click OK.
3. Click Components.
4. Enter the fluid components shown in the following table, and then click OK.

76 • Working with hydrates User Guide for Multiflash for Windows

 Component Amount (mol)

Methane 85.93

Ethane 6.75

Propane 3.13

Isobutane 0.71

Butane 0.88

Pentane 0.57

Carbon dioxide 1.31

Nitrogen 0.72

Water 10

5. In the Fluid composition panel, enter the amounts for each component, as shown in the previous
table.
6. On the Hydrates ribbon, click CPA Infochem, and then click OK on the message.
This automatically specifies the hydrates model with default settings.

7. In the Conditions area, enter the temperature as 270 K and the pressure as 1 MPa.

8. On the Home ribbon, click .

Results:
Hydrate2 is formed at the specified conditions. The output shows the amount of hydrate and gas phases
formed.

User Guide for Multiflash for Windows Working with hydrates • 77

FAQ:
Q: Why don't I get any hydrate formation with my own fluid?
A: Every system has its own properties and behaviour. There are several things you can try to obtain a
hydrate formation prediction.

1. Try the calculation again with a different quantity of water.

2. Check that you are using the appropriate hydrate phase in your calculation. By default, the
HYDRATE H phase is not included in your model. You can find a list of typical hydrate-forming
components and their hydrate phase type in Hydrate formation and inhibition models.
3. Generate the hydrate phase boundary so that you can see the areas of temperature and pressure
where your hydrate is likely to form, and then repeat the PT flash calculation with appropriate tem-

perature and pressure values. To do so, click Phase Envelope , select the appropriate
hydrate phase, select the basis as mole fraction, set the phase fraction to 0, and then click Plot.

If you are still unsuccessful, it is likely that your system does not form hydrates.
Q: Why is the calculation sensitive to the amount of water, and how do I know whether the amount
I have used is correct to give reliable results for my system?
A: At equilibrium conditions, water distribution among the different phases is determined by the model
used, and depends on the current temperature, pressure and global fluid composition. Ideally, you should
use the amount of water expected in the total global fluid composition of the system that you are model-
ling. Only in this case can the software estimate a rigorous phase distribution.
If you use too small an amount of water, you might find the water distributed among the fluid phases,
rather than forming a hydrate phase. If you use too large an amount of water, you might find that a
hydrate phase is predicted to form too readily.

78 • Working with hydrates User Guide for Multiflash for Windows

What else can I do?

1. To support your PT flash calculation, you should consider plotting the phase envelope for your
system to obtain an overview of its behaviour under different conditions.
2. You can add inhibitors and explore the effect on hydrate formation.

Calculating hydrate formation and dissociation

Problem:
What are the hydrate formation and dissociation temperatures at fixed pressure, and the formation and
dissociation pressures at fixed temperature?
The hydrate dissociation temperature is the temperature below which hydrates can form. The hydrate
dissociation calculation is an example of a fixed phase fraction flash.
The hydrate nucleation temperature is the temperature at which the nucleation of hydrates occurs and
hydrates can form. It is not strictly a PT flash calculation; rather, it is based on the stochastic behaviour
of how hydrate crystals form, and provides an estimate of the conditions that cause the hydrate crystals to
go from a meta-stable state and start to form.
Between the dissociation and nucleation temperatures is the area of hydrate risk where hydrates may or
may not form, depending on the time scale and kinetics of the formation process. The formation and disso-
ciation temperatures vary with pressure, as shown in the image. The hydrate dissociation curve is also
known as the equilibrium hydrate formation curve.

User Guide for Multiflash for Windows Working with hydrates • 79

Approach:

1. Define your fluid.

2. Specify the hydrate model with nucleation, so that you can calculate hydrate formation.
3. Perform fixed phase flash calculations at your required temperature and pressure.

For the following example, you can use the file hydrate.mfl, which describes a gas condensate, if you do
not want to enter the model and component data manually.
Try it yourself:

1. If you are using our example file, on the File menu, click Open, open the file hydrate.mfl, and
then proceed to step 7.
Tip: By default, the example files are in the MFL Files folder of the Multiflash installation.
2. On the Home ribbon, click Units, ensure that the input and output pressure units are MPa, the
input and output temperature units are K, the amount input units are mol, and the amount output
units are g, and then click OK.
3. Click Components.
4. Enter the fluid components shown in the following table, and then click OK.

Component Amount (mol)

Methane 85.93

Ethane 6.75

Propane 3.13

Isobutane 0.71

Butane 0.88

Pentane 0.57

Carbon dioxide 1.31

Nitrogen 0.72

Water 10

5. In the Fluid composition panel, enter the amounts for each component, as shown in the previous
table.
6. On the Hydrates ribbon, click CPA Infochem, and then click OK on the message.
This automatically specifies the hydrates model with default settings.

7. On the Models ribbon, click Select Model.

8. Check Phase Nucleation.
9. Click Define model, and then click OK on the message.
Rationale: You must specify phase nucleation when you are calculating formation of hydrates.
10. Click the Hydrates ribbon.
11. In the Conditions area, enter the temperature as 270 K and the pressure as 1 MPa.

80 • Working with hydrates User Guide for Multiflash for Windows

 12. To calculate the dissociation temperature at a pressure of 1 MPa, click .
Note: This shortcut performs a fixed phase flash at the specified pressure, and searches for the
most stable hydrate phase.
Result: HYDRATE2 is the most stable hydrate phase at the specified pressure, and the disso-
ciation temperature at 1 MPa is 276.15 K.

13. To calculate the dissociation pressure at a temperature of 270 K, click .

Note: This shortcut performs a fixed phase flash at the specified temperature, and searches for the
most stable hydrate phase.
Result: HYDRATE2 is the most stable hydrate phase at the specified temperature, and the disso-
ciation pressure at 270 K is 0.598 MPa.

User Guide for Multiflash for Windows Working with hydrates • 81

 14. On the Home ribbon, click .
15. To calculate the hydrate formation pressure at 270 K, in the Fixed Phase Fraction Flash dialog
box, enter the following values, and then click Calculate.

Item Value

Temperature 270

Phase Hydrate2

Basis Nucleation

Result: The hydrate formation pressure at 270 K is 1.26 MPa. The nucleation calculation is, in the
thermodynamic sense, inherently unstable, as reported.

82 • Working with hydrates User Guide for Multiflash for Windows

 16. On the Home ribbon, click .
17. To calculate the hydrate formation temperature at 1 MPa, in the Fixed Phase Fraction Flash dialog
box, enter the following values, and then click Calculate.

Item Value

Pressure 1

Phase Hydrate2

Basis Nucleation

Result: The hydrate formation temperature at 1 MPa is 268 K. The nucleation calculation is, in
the thermodynamic sense, inherently unstable, as reported.

User Guide for Multiflash for Windows Working with hydrates • 83

Results:

Fixed Hydrate formation value Hydrate dissociation value

Temperature (270 K) 1.26 MPa 0.598 MPa

Pressure (1 MPa) 268.04 K 276.15 K

FAQ:
Q: When I try to calculate the hydrate formation temperature, why do I get an error message like this:
20292 - Cannot find converged point - max. iterations
20024 - Cannot find starting point for calculation - there may be no solution
A: For hydrate formation calculations, this is most often because there is no hydrate phase at the
specified conditions. You can confirm this by plotting the phase boundaries for hydrate formation and
dissociation, as outlined next.
What else can I do?
To support your calculations, you should consider plotting the phase boundaries for hydrate formation
and dissociation, to obtain an overview of behaviour under different conditions. To do so, on the Main

ribbon, click , choose your hydrate phase, and then plot mole fraction (value 0) and nucleation
in turn.

84 • Working with hydrates User Guide for Multiflash for Windows

Determining maximum allowable water content
Problem:
What is the maximum amount of water that can be present in my fluid at a given pressure and temper-
ature before hydrates can form?
The tolerance calculation combines two mixtures in different ratios until a specified condition is met. The
following example finds the maximum water content for the mixture at 270 K and 1 MPa before hydrates
will form. The initial water content is zero, and this is increased until the initial formation of hydrate.
Approach:

1. Define your fluid.

2. Specify the hydrate model.
3. Perform a tolerance calculation at your required temperature and pressure.

Try it yourself:

1. If you are using our example file, on the File menu, click Open, open the file hydrate.mfl, and
then proceed to step 7.
Tip: By default, the example files are in the MFL Files folder of the Multiflash installation.
2. On the Home ribbon, click Units, ensure that the input and output pressure units are MPa, the
input and output temperature units are K, the amount input units are mol, and the amount output
units are g, and then click OK.
3. Click Components.
4. Enter the fluid components shown in the following table, and then click OK.

User Guide for Multiflash for Windows Working with hydrates • 85

 Component Amount (mol)

Methane 85.93

Ethane 6.75

Propane 3.13

Isobutane 0.71

Butane 0.88

Pentane 0.57

Carbon dioxide 1.31

Nitrogen 0.72

Water 0

5. In the Fluid composition panel, enter the amounts for each component, as shown in the previous
table.
6. On the Hydrates ribbon, click CPA Infochem, and then click OK on the message.
This automatically specifies the hydrates model with default settings.

7. If you are using our example file, in the Fluid composition panel, set the amount of water to 0.
8. In the Conditions area, ensure that the following values are entered.

Condition Value

Temperature 270 K

Pressure 1 MPa

9. On the Tools ribbon, click .

86 • Working with hydrates User Guide for Multiflash for Windows

 10. From the Select phase list, choose HYDRATE2, and then ensure that the molar phase fraction is
set to 0.
Rationale: The example file specifies a fluid that forms structure II hydrates.
11. On the Composition of Second Fluid tab, set the amount of water to 1.
12. Click Calculate, and then, in the Tolerance Result dialog, click Yes.
Result: The calculated amount of water is added to your fluid.
13. Click Close.
14. Check Total Amounts.
15. Scroll to the end of the Phase Compositions list, to see the maximum amount of water that can be
added to the original water-free stream to meet the condition of zero hydrate phase at the chosen P
and T.

User Guide for Multiflash for Windows Working with hydrates • 87

FAQ:
My calculation failed, where did I go wrong?
The tolerance calculation is a fixed phase calculation and might not have solution. if the calculation
fails, check that the specified temperature and pressure are within the hydrate phase envelope when the
system is saturated with water.

Adding inhibitors with the inhibitor calculator

Thermodynamic hydrate inhibitors decrease the temperature or increase the pressure at which hydrates
will form from a given gas mixture. In Multiflash, the CPA-based hydrate model includes parameters for
water with methanol, ethanol, MEG, DEG, TEG and salts.
To investigate the effect of an inhibitor, you include the inhibitor in the list of components for your
fluid. You can add inhibitors using either of the following methods:

Add it to the list of components in your fluid and specify the amount in the total mixture just as
for any other component.
Use the inhibitor calculator to calculate the amount of inhibitor or inhibitors to be added to the
amount of water present in the fluid in order to reach a user-defined inhibitor concentration.
Note: The inhibitor partitions between the different fluid phases present at equilibrium, and the
amount in a particular phase depends on the conditions and the amounts of other components. For
example, methanol will typically be present to a significant extent in the oil and gas phases, as
well as in the aqueous phase.

88 • Working with hydrates User Guide for Multiflash for Windows

The inhibitor calculator is included to simplify the addition of common inhibitors. The concentration can
be specified in mass, molar or volume units. When you use the inhibitor calculator, the components that
you specify are added automatically to the components list, along with the calculated amounts.
You can add components from both types of inhibitor (alcohols and salts) to the same fluid.
After you have added your chosen inhibitors, you can perform the full range of Multiflash calculations
on your fluid.
To add alcohols and glycols:

1. On the Hydrates ribbon, click .

2. Select a databank for the pure component properties.

3. Enter the amount of water to which the inhibitor is added.
Note: If you have already defined water in your fluid, the amount is shown in the Water Amount
field.

User Guide for Multiflash for Windows Working with hydrates • 89

 Tip: You can change the units used for the water by clicking Units.
4. Specify the units to use for inhibitor concentration.
Note: The inhibitors are added to your fluid in the selected input unit for the fluid, even if the
inhibitor concentration is specified in other units.
5. For each inhibitor that you want to add, enter the required concentration as a percentage of the
total amount of water plus inhibitors.
Restriction: The total percentages of all inhibitors must sum to less than 100.
Example: If you have 10 mol of water, and specify 10% methanol and 10% MEG, in mole %
units, the calculator adds 1.25 mol of each of the inhibitors (a total amount of 12.5 mol of the
three components).
6. Click Add.
Result: The inhibitors and amounts displayed in the Inhibitor Amounts dialog box are added to
the components of your fluid.
7. Remove the Inhibitor Amounts dialog box, and then click Close.

Salt calculator
Although you can include the ions in your component list by selecting them from INFODATA, it is
easier to use the inhibitor calculator to specify the concentration of various salts in water using
commonly-reported laboratory measurements.
When you add ions, the electrolyte model can only be selected as part of the hydrate model. The model
selection is made on the Hydrates tab, using CPA + Electrolytes.

90 • Working with hydrates User Guide for Multiflash for Windows

To add salts and ions:

1. On the Hydrates ribbon, click , and then click the Salts/Ions tab.

2. Select a databank for the pure component properties.

3. Enter the amount of water to which the inhibitor is added.
Note: If you have already defined water in your fluid, the amount is shown in the Water Amount
field.
Tip: You can change the units used for the water by clicking Units.
4. Click the tab for the analysis type that you have, and proceed as shown in the table.
Note: The inhibitors are added to your fluid in the selected input unit for the fluid, even if the
inhibitor concentration is specified in other units.

User Guide for Multiflash for Windows Working with hydrates • 91

 Analysis Procedure
type

Ion Analysis 1. Enter the amounts of each ion, in mg/l.

2. If you have a solution density measurement, enter the value, in gm/cc.
Restriction: You must enter both positive and negative ions.
3. Choose whether to include the effect of ions other than Na+, K+, Ca2+,
Cl- and Br- as an equivalent amount of all those ions, or as equivalent
Na+ and Cl- ions only.

Total 1. Enter the total dissolved solid, in mg/l.

dissolved
2. If you have a solution density measurement, enter the value, in gm/cc.
solids (TDS)

Salt 1. Choose the salt analysis units.

Analysis
2. Enter the amounts of each salt.
3. Choose whether to include the effect of ions other than Na+, K+, Ca2+,
Cl- and Br- as an equivalent amount of all those ions, or as equivalent
Na+ and Cl- ions only.

5. Click Add.
Note: If you enter values on more than one analysis option, the amount of salt to be added will be
taken from the visible tab.
Result: The inhibitors and amounts displayed in the Inhibitor Amounts dialog box are added to
the components of your fluid.
6. Remove the Inhibitor Amounts dialog box, and then click Close.

Calculating inhibitor amounts required to

suppress hydrate formation
Problem:
How much inhibitor do I need to suppress hydrate formation at a given temperature and pressure?
Approach:

1. Define your fluid.

2. Specify the hydrate model.
3. Use the inhibitor dosage tool to calculate the required amount of a single inhibitor.
Note: This is another example of a tolerance calculation. If you have a mixture of inhibitors, use
the tolerance calculation tool, where you can specify an inhibitor mixture.

For the following example, you can use the file hydrate.mfl, which describes a gas condensate, if you do
not want to enter the model and component data manually.

92 • Working with hydrates User Guide for Multiflash for Windows

Try it yourself:

1. If you are using our example file, on the File menu, click Open, open the file hydrate.mfl, and
then proceed to step 7.
Tip: By default, the example files are in the MFL Files folder of the Multiflash installation.
2. On the Home ribbon, click Units, ensure that the input and output pressure units are MPa, the
input and output temperature units are K, the amount input units are mol, and the amount output
units are g, and then click OK.
3. Click Components.
4. Enter the fluid components shown in the following table, and then click OK.

Component Amount (mol)

Methane 85.93

Ethane 6.75

Propane 3.13

Isobutane 0.71

Butane 0.88

Pentane 0.57

Carbon dioxide 1.31

Nitrogen 0.72

Water 10

5. In the Fluid composition panel, enter the amounts for each component, as shown in the previous
table.
6. On the Hydrates ribbon, click CPA Infochem, and then click OK on the message.
This automatically specifies the hydrates model with default settings.

7. In the Conditions area, enter the temperature as 270 K and the pressure as 1 MPa.
Rationale: We know from the same example fluid that, at this temperature and pressure, hydrates
form. See Calculating hydrate formation at a given pressure and temperature.
8. On the Home ribbon, click Components, and then add Methanol as a component.
You are using methanol as an inhibitor.
Tip: If you have a fluid that already contains an amount of your inhibitor, you need not set the
amount to 0; the inhibitor dosage tool takes account of the existing amount , and adds only the
extra amount of inhibitor required.

9. On the Hydrates ribbon, click .

10. In the Calculator Inhibitor Amount dialog box, enter the purity as 100%.
11. In the Hydrate list, select HYDRATE2.

User Guide for Multiflash for Windows Working with hydrates • 93

 12. Click Calculate, and then, on the Tolerance Result dialog box, click OK.
Result: The required inhibitor amount is displayed in the Amount Required field.
13. Click Close.
14. Check Total Amounts.
15. Scroll to the end of the Phase Compositions list, to see the amount of methanol required to meet
the condition of zero hydrate phase at the chosen P and T.

After the inhibitors are added to the system, you can check the hydrate phase boundary to see the hydrate
inhibition effect and the partitioning of the inhibitors among the fluid phases by performing a flash calcu-
lation at a given T and P. You can find a worked example in Looking at the effect of inhibitors.

Looking at the effect of inhibitors

Problem:
What is the effect on hydrate dissociation of adding an inhibitor?
Approach:

1. Define your fluid.

2. Calculate the hydrate phase boundary.
3. Add your inhibitor.
4. Calculate the hydrate phase boundary and compare it with the previous boundary.

For the following example, you can use the file hydrate.mfl, which describes a gas condensate, if you do
not want to enter the model and component data manually.

94 • Working with hydrates User Guide for Multiflash for Windows

Try it yourself:

1. If you are using our example file, on the File menu, click Open, open the file hydrate.mfl, and
then proceed to step 7.
Tip: By default, the example files are in the MFL Files folder of the Multiflash installation.
2. On the Home ribbon, click Units, ensure that the input and output pressure units are MPa, the
input and output temperature units are K, the amount input units are mol, and the amount output
units are g, and then click OK.
3. Click Components.
4. Enter the fluid components shown in the following table, and then click OK.

Component Amount (mol)

Methane 85.93

Ethane 6.75

Propane 3.13

Isobutane 0.71

Butane 0.88

Pentane 0.57

Carbon dioxide 1.31

Nitrogen 0.72

Water 10

5. In the Fluid composition panel, enter the amounts for each component, as shown in the previous
table.
6. On the Hydrates ribbon, click CPA Infochem, and then click OK on the message.
This automatically specifies the hydrates model with default settings.

7. On the Home ribbon, click .

8. In the Phase Envelope dialog box, on the Phases tab, set the values shown in the table.

Item Value

Type of solution Normal

Select Phase Hydrate2

Select Basis Mole fraction

Phase fraction 0

9. Click Plot, and then click No in the message.

User Guide for Multiflash for Windows Working with hydrates • 95

 10. Remove the Phase Envelope dialog box.
Important: Do not clear the plot because you will compare this later.

11. On the Hydrates ribbon, click .

12. In the Methanol field, enter 10.

Tip: For your own calculations, you can specify the inhibitor concentration as mass %, mole % or
volume %. This example has units of mass %.
13. Click Add, remove the Inhibitor Amounts dialog box, and then click Close.

14. On the Home ribbon, click .

15. Enter the same values as previously, and then click Plot.
16. Repeat the addition of inhibitor, using 20% methanol.

96 • Working with hydrates User Guide for Multiflash for Windows

 17. Plot the phase boundary again.

As more inhibitor is added, you can see that, for a given pressure, the hydrate dissociation temperature is
reduced.
What else can I do?

1. Perform a series of fixed phase flashes or boundary plots, varying the inhibitor type and amount,
to see the trends in inhibitor effect.
2. You can see the effect of salts on the hydrate dissociation by following the procedure above, but
using a salt solution as the inhibitor instead of methanol. Enter the following salt analysis data
into the inhibitor calculator, to add salts to your fluid, and then plot the phase boundary as before.
Tip: Do not forget to change the hydrate model to CPA + Electrolytes.

Salt Mass % in Solution

NaCl 6.993

CaCl2 0.735

MgCl2 0.186

KCl 0.066

SrCl2 0.099

BaCl2 0.036

You should obtain these phase boundary plots if you use the hydrate.mfl file:

User Guide for Multiflash for Windows Working with hydrates • 97

 3. If your fluid has only a trace amount of water, it might be more effective to dehydrate your system
to inhibit hydrate formation rather than add inhibitor. To investigate this, perform a maximum
water content calculation to see if it is more effective to remove the excess water or add your
inhibitor.

Scale precipitation
Problem:
Is there any scale precipitation in my hydrate system?
Salt injection represents a powerful hydrate inhibition strategy. However, salts themselves can also intro-
duce problems, for example, scale formation. Given the presence of salts in the mixture, Multiflash can
determine whether there is any scale precipitation at given conditions, or, for a given amount of salts in
the mixture, the conditions at which there might be scale precipitation.
Note: The salt precipitation model is a simple model to predict the salt precipitation together with
hydrate formation and inhibitition. The model is not suitable for comprehensive water analysis.
Approach:

1. Define your fluid.

2. Specify scale precipitation calculations in your model.
3. Perform a standard flash or fixed phase flash to calculate the phases in your fluid.

For the following example, you can use the file scaling.mfl, which describes a gas condensate, if you do
not want to enter the model and component data manually.

98 • Working with hydrates User Guide for Multiflash for Windows

Try it yourself:

1. If you are using our example file, on the File menu, click Open, open the file scaling.mfl, and then
proceed to step 11.
Tip: By default, the example files are in the MFL Files folder of the Multiflash installation.
2. On the Home ribbon, click Units, ensure that the input and output pressure units are MPa, the
input and output temperature units are K, the amount input units are mol, and the amount output
units are g, and then click OK.
3. Click Components.
4. Enter the fluid components shown in the following table, and then click OK.

Component Amount (mol)

Methane 85.93

Ethane 6.75

Propane 3.13

Isobutane 0.71

Butane 0.88

Pentane 0.57

Carbon dioxide 1.31

Nitrogen 0.72

Water 10

5. In the Fluid composition panel, enter the amounts for each component, as shown in the previous
table.
6. On the Hydrates ribbon, click CPA + Electrolytes, and then click OK on the message.
This automatically specifies the hydrates model with default settings for calculations including
salts.

7. On the Models ribbon, click .

8. In the Phases panel, check Halide Scales.
9. Click Define Model.
10. On the success message, click OK.

11. On the Hydrates ribbon, click .

12. Select the Salts/Ions tab, and then the Salt Analysis tab, and enter the salt analysis shown in the
table.

User Guide for Multiflash for Windows Working with hydrates • 99

 Salt Mass % in Solution

NaCl 6.993

CaCl2 0.735

MgCl2 0.186

KCl 0.066

SrCl2 0.099

BaCl2 0.036

13. Click Add, close the Inhibitor Amounts message, and then click Close.
14. In the Conditions area, enter the temperature as 270 K and the pressure as 1 MPa.

15. On the Home ribbon, click .

Result: Under the current conditions, the temperature is too high for any scale precipitation.
16. To calculate the temperature at which Nacl.2(H2 0) precipitation occurs at a pressure of 1 MPa, in
the Fixed Phase Fraction Flash dialog box, enter the following values, and then click Calculate.

Item Value

Pressure 1

Phase NACL.2(H20)

Basis Mole Fraction

Enter phase fraction 0

Result: The Nacl.2(H2 0) precipitation temperature at 1 MPa is 259.9 K.

100 • Working with hydrates User Guide for Multiflash for Windows
 17. Repeat the calculation for the precipitation of CaCl2 .6(H2 O).
Result: The CaCl2 .6(H2 O) precipitation temperature at 1 MPa is 240.6 K. At this temperature,
precipitation of KCL and Nacl.2(H2 0) also occurs.

User Guide for Multiflash for Windows Working with hydrates • 101
What else can I do?
A realistic scenario occurs if the salt concentration is higher, for example, 30 wt% equivalent of NaCl. A
flash at a temperature higher than hydrate dissociation conditions shows NaCl formation, whereas at a
temperature where a hydrate phase is present, NaCl.2(H2O) forms. You can do this as follows:

1. Using the scaling.mfl file, modify the salt analysis in the inhibitor calculator so that only 30 wt %
of NaCl is present.
2. Do a fixed phase flash at a pressure of 1 MPa to find the hydrate dissociation temperature (260.7
K).
3. Do a PT flash at a pressure of 1 MPa and 280 K and see NaCl formation.
4. Do a PT flash at a pressure of 1 MPa and 250 K and see NaCl.2(H2 O) formation.

102 • Working with hydrates User Guide for Multiflash for Windows