Ternary VLE Help

SimSci
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7HUQDU\0L[WXUH3ORWV
May 2014
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Table of Contents
Introduction ........................................................................................................ 1
Files .................................................................................................................... 1
Compatibility ..................................................................................................... 1
Initializing Office 2003 ...................................................................................... 1
Initializing Office 2007 ...................................................................................... 2
Comments .......................................................................................................... 3
Open Issues ............................................................................................................ 4
Limitations ............................................................................................................. 4
OFFICE 2003 ................................................................................................................... 5
THE VLLE-PLOT FUNCTIONS................................................................................... 5
The VLLE-Plot Main Commandbar ...................................................................... 5
The VLLE-Plot Ternary Cursor Commandbar ...................................................... 7
DETAILED DESCRIPTIONS ..............................................................................................10
VLLE-Plot Main Bar .................................................................................................10
PRO/II Database Group ........................................................................................10
Select PRO/II Database .....................................................................................10
System Definition Group ......................................................................................11
Select the mixture components .........................................................................11
Specify the system thermodynamic set .............................................................12
Specify the system pressure ..............................................................................12
Ternary Surface Plot Group ..................................................................................13
Plot a 3d-boiling surface ...................................................................................13
Binary VLLE Plots Window .............................................................................14
Ternary VLLE Plot Group ....................................................................................16
Create a Ternary Chart ......................................................................................16
Residue Curve Management Group ......................................................................21

Specify starting points for multiple Residue Curves .........................................21
PRO/II Model Results Group ................................................................................23
Plot PRO/II Column Profiles ............................................................................23
Plot PRO/II Streams ..........................................................................................24
Workbook Group ..................................................................................................25
Open a new Workbook .....................................................................................25
Remove Curve Series from Worksheets, Chart and Legend ............................25
VLLE-Plotbar Management Group.......................................................................26
Collapse the VLLE-Plot toolbar........................................................................26
Remove the VLLE-Plot toolbar ........................................................................26
The VLLE Ternary Cursor Commandbar .................................................................26
Ternary Cursor Group ...........................................................................................27
Movement direction of the ternary cursor in the upward direction ...................27
Movement direction of the ternary cursor in the downward direction ..............27
Movement direction of the ternary cursor in the leftward direction..................27
Movement direction of the ternary cursor in the rightward direction ...............27
Specify the Stepsize of the Ternary Cursor .......................................................27
Swap Binary Pair Group .......................................................................................28
Swap the pair along the diagonal Axis ..............................................................28
Swap the pair along the vertical Axis................................................................29
Swap the pair along the horizontal Axis ...........................................................29
Plot Style Group ....................................................................................................29
Specify the Color of Point-Flash lines and Residue Curves..............................29
Specify the Symbol Style of point flash curves ................................................30
Specify whether Curves are Added to the Legend or not ..................................30
Residue Curve Group ............................................................................................30
Generate a Point-Residue Curve .......................................................................31
Point Flash Group .................................................................................................31

Perform a single Point-Flash at the location of the Ternary Cursor ..................31
Specify the Colour of Point-Flash lines and Residue Curves............................32
Specify the modus of Point-Flashes ..................................................................33
Specify whether a Point-Flash is just calculated or also plotted .......................34
Specify System-Temperature for Fixed Temperature Point-Flashes ................35
The Ternary Cursor Hide/Show Group .................................................................35
OFFICE 2007 ..................................................................................................................35
THE VLLE-PLOT FUNCTIONS..................................................................................35
The VLLE-Plot Main Command bar ....................................................................35
The VLLE-Plot Ternary Cursor Commandbar .....................................................37
DETAILED DESCRIPTIONS ..............................................................................................40
VLLE-Plot Main Bar .................................................................................................40
PRO/II Database Group ........................................................................................40
Select PRO/II Database .....................................................................................40
System Definition Group ......................................................................................41
Select the mixture components .........................................................................41
Specify the system thermodynamic set .............................................................42
Specify the system pressure ..............................................................................43
Ternary Surface Plot Group ..................................................................................43
Plot a 3d-boiling surface ...................................................................................43
Binary VLLE Plots Window .............................................................................45
Ternary VLLE Plot Group ....................................................................................47
Create a Ternary Chart ......................................................................................47
Azeotropes Settings...........................................................................................50
Residue Curve Settings .....................................................................................50
Perturbing binary Azeotropic ............................................................................51
LLE-Settings .....................................................................................................51
Residue Curve Management Group ......................................................................52

Specify starting points for multiple Residue Curves .........................................52
PRO/II Model Results Group ................................................................................53
Plot PRO/II Column Profiles ............................................................................53
Plot PRO/II Streams ..........................................................................................54
Workbook Group ..................................................................................................55
Open a new Workbook .....................................................................................56
Remove Curve Series from Worksheets, Chart and Legend ............................56
VLLE-Plotbar Management Group.......................................................................57
Collapse the VLLE-Plot toolbar........................................................................57
Remove the VLLE-Plot toolbar ........................................................................57
The VLLE Ternary Cursor Command bar ................................................................57
Ternary Cursor Group ...........................................................................................57
Movement direction of the ternary cursor in the upward direction ...................57
Movement direction of the ternary cursor in the downward direction ..............58
Movement direction of the ternary cursor in the leftward direction..................58
Movement direction of the ternary cursor in the rightward direction ...............58
Specify the Stepsize of the Ternary Cursor .......................................................58
Swap Binary Pair Group .......................................................................................59
Swap the pair along the diagonal Axis ..............................................................59
Swap the pair along the vertical Axis................................................................59
Swap the pair along the horizontal Axis ...........................................................60
Plot Style Group ....................................................................................................60
Specify the Symbol Style of point flash curves ................................................61
Specify whether Curves are Added to the Legend or not ..................................61
Residue Curve Group ............................................................................................61
Generate a Point-Residue Curve .......................................................................61
Point Flash Group .................................................................................................62

Perform a single Point-Flash at the location of the Ternary Cursor ..................62
Specify the modus of Point-Flashes ..................................................................64
Specify whether a Point-Flash is just calculated or also plotted .......................65
Specify System-Temperature for Fixed Temperature Point-Flashes ................65
The Ternary Cursor Hide/Show Group .................................................................66

Introduction This example application will enable you to calculate and display ternary
mixture properties and simulation-results of ternary-system processes. A first
glance through the following pages gives you an overview of the graphical plot-
features. Also quaternary mixture properties can be calculated, although the
graphical display of these systems is not supported by ExcelTM. A special
tetrahedron plotter was written to this purpose, but will not be discussed in this
paper.
Files Source: Ternary_VLE.XLA
PRO/II Example: Azeo_a3-splitter.prz
AZEO_A3-SPLITTER.INP
Documentation: Ternary VLE Help.pdf
Compatibility This macro was tested using Windows Vista and XP, Office 2003 and 2007
Professional-US version, PRO/II 9.
Initializing Office To initialize the Excel-Addin, please complete the following steps
2003
1. Start PRO/II
2. File NEW
3. Import the keyword file Azeo_a3-splitter.inp
Solve and Save the Flowsheet
Quit PRO/II
4. Open Ternary_VLE.XLA
5. Select TOOLS>PRO/II>VLLE Plotbar
6. Confirm positively to the dialogue boxes:
PRO/II Ternary Mixture Plots 1

enable macros
Continue to the Welcome Window
7. Two new VLLE-Plot command bar appear.
Initializing Office Before starting with this addin, ensure that the Trust Access to the VBA project
2007 object model is checked in the developer macro settings
To initialize the Excel-Addin, please complete the following steps
1. Start PRO/II
2. File NEW
3. Import the keyword file Azeo_a3-splitter.inp
Solve and Save the Flowsheet
Quit PRO/II
4. Open Ternary_VLE.XLA
5. Select Add-Ins>PRO/II>VLLE Plotbar

Continue to the Welcome Window
6. The VLLE-Plot command bar appears.
Comments The VLLE-plotbar of the plotbar offers powerful functions to analyse ternary
mixture VLLE-equilibria. This includes
ternary boiling surface plot
binary boiling- and dewpoint curves
azeotropes
residue curves
point flashes
PRO/II column profiles and stream compositions
Toolbar and Worksheet management

Attention is directed to the Ternary Cursor in the center of the ternary diagram.
The Ternary Cursor allows the user to specify locations, ie. Compositions, in the
diagram. Later, and as explained in subsequent chapters, thermodynamic actions
can be performed to those compositions. As will be seen, the Ternary Cursor is a
powerful tool to query and investigate the thermodynamic equilibria of a given
system.
All functions on the VLLE-Plot commandbar are described in the following
chapters.
Open Issues
1. Saddle points are not guaranteed to be detected.
2. On the 3d-surface plot it is difficult to assign the components to the axes.

Indicating component name at each vertex of 3D diagram is not supported.
Limitations
1. Units of Measure in the PRO/II Database file must be
C for temperature
Bar for pressure
Using other units of measure in the PRO/II database file will produce wrong
results.
2. Any components assigned to only Vapour-Liquid Phase must be listed first in

the PRO/II Database file. E.g., the component CLFR, which is assigned only to
Vapour-Liquid phase is listed first, see picture below.
Ignoring this will deliver wrong results. This is very important!
3. The number of components selected in the PRO/II Database file must not exceed
20 (twenty).

Office 2003
The VLLE-Plot functions

The VLLE-Plot Main Commandbar
Symbol Description
PRO/II File Group
define system
System Definition Group
Select the mixture components
Select thermodynamic system
Specify system pressure. Unit of

measure is bound to kPa.
Ternary Surface Plot Group
Plot a 3d-boiling surface.
Binary VLLE Plots Group
Plot binary VLLE. This covers bubble

and dewpoint lines of each of the
existing binary system pairs that can
be composed.
Ternary VLLE Plot Group
Configure and generate a ternary

system plot including azeotropes,
Residue curves, boundary distillation

curves, tielines and binodal curve.
Residue Curve Management Group
Specify starting points for multiple

Residue Curves, be they distributed
parallel the binary axes or close to
existing azeotropes resulting in
boundary distillation curves.
PRO/II Results Group
Plot column profiles of towers

available in PRO/II model
Plot streams available in PRO/II

model
Workbook Group
Open a new Workbook
Clear the contents of worksheets and

remove the respective curves and
legend entries from the diagram.
VLLE-Plotbar Management Group
toggling to Collapses/expands the toolbar
Remove the toolbar from Excel

The VLLE-Plot Ternary Cursor Commandbar
Ternary Cursor Group
Movement direction of ternary

cursor
Specify stepsize for movements of

the Ternary Cursor. The numbers
refer to molar fractions.
Swap Binary Group
Swaps the binary pair located on the

diagonal axis

vertical axis

horizontal axis
Ternary Cursor Action Group
Specify the color of point flash and

residual curves.

Specify the symbol style of point
flash curves
Specify whether curves are added

to the legend or not.
Residue Curve Group
Generate a Point-Residue Curve at

the location of the Ternary Cursor.
Point Flash Group
Performa single Point-Flash at the

location of the Ternary Cursor
Specify the Flash-Type, ie. Whether

a bubblepoint, a dewpoint or a fixed
temperature flash must be
performed.
Specify the modus of Point-Flashes.

In Progressive mode the resulting
vapour or liquid composition (this
depends of flash-type) will be
passed to the Ternary Cursor. Use
Single to devoke this modus,

Specify whether a Point-Flash is
just calculated or also plotted.
Specify System-Temperature for

Fixed Temperature Point-
Flashes . This is only enabled
for Fixed Temperature-Flashes.
Otherwise it serves as
temperature indicator.
Hide/Show Ternary Cursor

Group
toggling to
Hide/Show the Ternary Cursor

toggling to from the chart
Note: Using the mouse, the user can re-arrange the large toolbar so the control
elements are positioned onto more lines.

Detailed Descriptions
VLLE-Plot Main Bar
The VLLE-Plot Main Bar supports the generation of binary and ternary
diagrams that display ternary mixture Vapour-Liquid-Liquid Equilibria
(VLLE) data. This includes
ternary boiling surface
plot binary boiling- and dewpoint curves
azeotropes
residue curves
tielines and binodal curve
It also allows access to PRO/II simulation results, ie.
PRO/II column profiles
stream compositions
Finally, in order to better manage the toolbar, which becomes part of the
Excel-Toolbar set, it allows
Toolbar and Worksheeet management
PRO/II Database Group
The PRO/II Database Group supports all user actions that relate to
specifying a PRO/II database file with the proper thermodynamical data,
be it components and thermodynamic sets.
Hitting the control will open the PRO/II File Window.

Select PRO/II
Database

After browsing for the PRO/II Database file, hit Connect.
Note: The PRO/II file serves as the container for components, thermodynamic
sets, columns and streams.
! Please ensure that in deg Celsius and Bar are selected as units of measure
The user may intend to add new VLLE data onto a ternary diagram that had been
generated earlier by using the VLLE Ternary Plot feature. In this case, the respective
workbook would need to be loaded into Excel, first. Hitting , the
PRO/II File window will now look slightly different. Having detected that a workbook
already exists, the window will allow to simply connect to the respective PRO/II file that
had been specified when the workbook had been initialized.
This feature allows the user to continue working with existing ternary diagrams.
The System Definition Group supports all user actions that relate to
specifying the system be it components, the thermodynamic method and
the system pressure.
Note: Currently all VLLE-calculations are performed at constant pressure
Hitting the control will open the System Definition Window.

Select the mixture
components

The components available in the connected PRO/II Database will show in
the dropdowns.
The dropdown controls are positioned according to the component
locations on the ternary plot.
After closing this window, all control elements in the VLLE-Plot toolbar
become enabled.
Note: The user can always change the components to superimpose ternary maps.
This is a powerful way to compare alternative candidates for entrainers.
Currently, the number of components is fixed to three.
Note: The macro has inbuilt functionality to support quaternary systems. This
feature is currently not available.
Acting on the control will display the thermodynamic

Specify the
sets available in the PRO/II Database.
system The options include all thermodynamic sets available in the connected
thermodynamic PRO/II Database file, e.g.,
set
Note: The user can always change the thermodynamic set to superimpose ternary
maps. This is a powerful way to compare alternative thermodynamic sets, such as
sets with alternative binary interaction parameters, or alternative configurations
with respect to the methods.
Note: Each time a Thermo-Set is is selected it is passed to sheet "mngr", cell

A1. When performing flashes, the internal subroutine will retrieve the
thermo-set from this cell.
The control allows to enter and specify the system pressure.

Specify the Note: The user can always change the system pressure to superimpose ternary
system pressure maps. This is a powerful way to compare alternative system pressures.

Note: Each time a new pressure value is entered it is passed to sheet "Flash",
cell C3. When performing flashes, the internal subroutine will retrieve the
pressure specification from this cell.
The Ternary Surface Plot Group supports all user actions that relate to 3d-
charts showing either the dewpoint plane or the boiling point plane.
Hitting the control will open the Boiling Surface Window.

Plot a 3d-boiling
surface
The no. of Grid-points entry allows to specify the number of flash-

calculations along each binary axis.
Bubble- and Dew-point surfaces can be specified.
A 3d-plot exhibiting the boiling surface will be generated in Chart "3D"
Use the controls at lower right section of the chart to rotate the plot.
Note: The surface map allows an intuitive overview on the system. It quickly
tells you whether azeotropes or tielines are to be expected.

The above plots show the bubble- and dewpoint planes for the system
H2O-IPA-CH at 101.3 kPa using a grid of 52 datapoints.
While the bubble-point surface (left) indicates the LLE-region, the
dewpoint surface (right) indicates the location of the ternary azeotrope.
Numerical data are located in Sheets "t_1" and "t_2".
Data Container Sheet t_1:
Sheet t-2:
Data Container
The Binary VLLE Plot Group supports all user actions that relate to binary
VLLE-plots showing both the dewpoint curve and the boiling point curve.
Hitting the control will open the Binary VLLE Plots Window.
Binary VLLE
Plots Window

The No. of Points entry allows to specify the number of flash-calculations
along each binary axis.
A 2d-plot exhibiting bubble- and dewpoint curves for each of the binary
pairs will be generated in Chart "TXY"
H2O-IPA-CH
PRO/II Binary BVLE
157.01 157.01
145.45 145.45
133.90 133.90
H2O-IPA Boilingpoints 101.3 kPa ALC_VLLE

122.34 122.34 H2O-IPA Dewpoints 101.3 kPa ALC_VLLE
Temperature [C]
H2O-CH Boilingpoints 101.3 kPa ALC_VLLE

H2O-CH Dewpoints 101.3 kPa ALC_VLLE
IPA-CH Boilingpoints 101.3 kPa ALC_VLLE
110.78 110.78 IPA-CH Dewpoints 101.3 kPa ALC_VLLE
H2O-IPA Boilingpoints 500 kPa ALC_VLLE
H2O-IPA Dewpoints 500 kPa ALC_VLLE
H2O-CH Boilingpoints 500 kPa ALC_VLLE
99.23 99.23 H2O-CH Dewpoints 500 kPa ALC_VLLE
IPA-CH Boilingpoints 500 kPa ALC_VLLE
IPA-CH Dewpoints 500 kPa ALC_VLLE
Reihe1
87.67 87.67
76.11 76.11
64.56 64.56
53.00 53.00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x [-]
The chart above shows bubble and dewpoint curves for the three available
binary pairs of the system H2O, IPA and CH. The curves were requested
at 101.3 kPa and 500 kPa using the "Append" option. It can be seen how
the H2O-CH Azeotrope (blue lines) moves to the right at the higher
pressure while the IPA-CH Azeotrope (red lines) moves to the left.
Note: The binary curves allow an intuitive overview on the system. It quickly
Data Container Numerical data are located in Sheet "BVLE"

The Ternary VLLE Plot Group supports all user actions that relate to
ternary diagrams showing azeotropes, tielines and Residue Curves.
Hitting the control will open the Ternary Plot Window.

Create a Ternary
Chart

This window is composed of four main sections:
Integration Settings for Residue Curves
Integration Settings for Azeotropes
Integration Setting for Tielines and Binodal Curve
Configuration of the Plot
A typical Ternary Plot exhibiting binary and ternary azeotropes, tielines

and binodal curve is shown below. This plot was produced using the
default settings and by configuring the plot as shown in the Plot-Options
box.

H2O-IPA-CH
1
PRO/II Ternary Calculations
0.9
0.8
0.7
0.6
CH - IPA
Ternary-Cursor
Binary Azeotrope, 101.3 kPa, ALC_VLLE
0.5
Ternary Azeotrope, 101.3 kPa, ALC_VLLE
0.4 Binodal Curve, 101.3 kPa, ALC_VLLE
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
Note: To compute Residue curves, the user is advised to generate starting points
for Residue curves first. Use the button , which is explained in next
chapter.
Isothermal Tielines
Option Depending on the settings in the LLE Settings tieleines are generated at the
bubblepoint or, alternatively, at isothermal conditions. For isothermal
tielines, the user must activate the Isothermal Radio-Button. A
Temperature entry box appears for the specification of the temperature.
The plot is generated in Charz "2D"

The numerical data are stored in sheets
Sheet "AZP"
o Azeotropic points
Data Container
Sheet "LLE"
Data Container
o Tielines and binodal curve
Sheet "RC"
o Residue curves
Data Container
Technical Technical Reference

References
Azeotropes Settings
Azeotropes are calculated iteratively by minimizing the expression

(1) y-x
for all three components in the ternary system.

Technical Reference
Azeotropes Settings:
Azeotropes
Label Description Range good value
Max. Iter. : The maximum number of iterations for the 0<i<inf 100
minimization
Tolerance : An internal tolerance 0<tol<1 .0001
Technical Reference
Residue Curve Settings
Residue Curves are calculated by using eq. 15 in Doherty, Perkins, On

the Dynamics of Distillation Processes-I, page 283, Chem. Eng. Science,
1978, vol 33 pp281-301.
The equation results in:
(1) d_x/d_ksi= x -y
(2) x_new=x_old + (x_old-y_old)*ksi
where x_new and x_old are two successive points of the curve, x_new being
calculated as a function of the old x and y and the integration constant ksi.
x and y are mole fractions of the mixture.

Enter the settings for the numerical calculations in the Integration
Settings entry-group.
Integration Settings:
ksi : its the integration constant ksi in eq. (2) 0<ksi<1 0.4
Note: ksi=1 will result in Distillation Curve
Calculations instead of Residue Curves Calcs. In
case of binaries these would be McCabe Thiele
100% Steps between bubble- and dew-curve. Here
it would be 100% steps between bubble- and dew-
plane. For narrow boiling systems ksi=1 is ok. In
other cases make ksi smaller than lets say 0.3.
ksi-min : Although you fix the value for ksi, ksi would get 0<ksi<1 0.005
reduced artificially by the calculation engine
whenever the ksi-value results in negative
compositions. The entry for ksi-min marks the
minimum value the integration constant ksi in eq.
(2) would get assigned by the calculation engine.
Min. Iter. : The minimum number of points to be calculated for 0<i<inf 10

each residue curve.
Max. Iter. : The maximum number of points to be calculated for min. It<i<inf 50
each residue curve
Tolerance : If the difference between x_new and x_old gets 0<tol<1 .0001
smaller than Tolerance, calculations are stopped.
This normally marks an azeotrope or a pure
component corner.
1. In order to calculate residue-curves you must define a grid of

starting points, first.. Use the control to do that.
Technical Reference Technical Reference

Perturbing Azeotropes Perturbing binary Azeotropic

Perturbance of Perturbing binary Azeotropic compositions delivers 0<pert<1 1e-4
Azeotrope new ternary compositions, which if you route a
residue curve through this point, behave similar
though not necessarily exactly like boundary
residue curves. The azeotropic composition is
perturbed by the molar fraction of the third
component according the entry field, i.e. this value
is used as molefrac of the third component.
Note: Specifying small values for perturbance
serves as a first approach to approximate
boundary residue curves.
In order to calculate residue-curves that pass through perturbed binary

azeotropes, you must have to define these points, first. Use the
control to do that.

LLE Tielines and LLE-Settings
Binodal Curve
LLE-Calculations generate the tielines and the binodal curve.
The calculations consist of repeated two-liquid-phase flashes. Flash
compositions are always calculated as function of a given tieliene's length
and its midpoint, using the formula:
(3) x_new=x_midpoint + orthogonal step
(4) orthogonal step = percentage of the tieline-length
This is repeated until x_new lies outside the two-phase region.

LLE-Settings:
Max. Number The maximum number of tielines to be calculated 0<i<inf 50
th
Display Show only every i tieline o<=i<infinite 5
Frequency
% orthogonal Percentage of the tieline length at which the next 0< 5
steps composition point will be located orthogonally from perc<100
the momentary composition point.
The Residue Curve Management Group supports all user actions that
relate to the generation of starting points for Residue Curves.
Hitting the control will open the Residue Curve Starting Points
Specify starting Window.
points for multiple
Residue Curves
The user has two options:

a) Hit Add Grid in order to distribute starting points (specify the no.)
parallel to the binary axes (specify distance). This option prepares the
generation of a geometrically build up residue curve map.

1
0.9
0.8
0.7
0.6
Ternary-Cursor
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Note: The red starting points will disappear after the Residue Curves have been
calculated.
b) Hit Perturb Azeotropes in order to position starting points right next to
existing binary azeotropes. This option prepares the generation of residue
curves that come very close to boundary distillation curves. The amount of
perturbation of the binary mixture into the ternary region is according to
the value specified in . An exact mathematical procedure for
detecting the location of boundary curves, involves a deeper analysis
Note: The blue line is only temporary and has no thermodynamic meaning. This
line and also the blue starting points will disappear after the boundary
distillation curves have been calculated.
After generating the starting points use either or in

order to generate the Residue curves. The resulting maps for GRID and Perturb
Azeotropes A
H2O-IPA-CH H2O-IPA-CH
1 1
PRO/II Ternary Calculations PRO/II Ternary Calculations
0.9 0.9
0.8 0.8
0.7 0.7
0.6 0.6
Ternary-Cursor
CH - IPA
CH - IPA
Ternary-Cursor
0.5 Binary Azeotrope, 101.3 kPa, ALC_VLLE
Binodal Curve, 101.3 kPa, ALC_VLLE
Separatrix, 101.3 kPa, ALC_VLLE
0.4 Binodal Curve, 101.3 kPa, ALC_VLLE 0.4 Separatrix, 101.3 kPa, ALC_VLLE
0.3 0.3
0.2 0.2
0.1 0.1
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O CH - H2O
The generated Starting points are saved on sheet "GRID"
Data Container

PRO/II Model Results Group
The PRO/II Model Results Group supports all user actions that relate to
retrieving simulation model data from connected PRO/II models.
Note: This powerful feature enables the engineer to review his model results
within the thermodynamic context. It allows him or her to to gain full control on
the simulation model results.
Hitting the control will open the PRO/II Column Selection

Window.
Plot PRO/II
Column Profiles
The Plot below shows the Vapour profile of Column T-2 in PRO/II Model
Azeo_a3-splitter.prz. It is clearly indicated that the overhead vapour
product is close to the ternary azeotrope, while the bottom (vapour)
composition is almost pure IPA.
The fact that the profile slightly crosses the boundary distillation curve is
explained by slightly different pressures in tower operation and Residue
curve map.
H2O-IPA-CH
1
0.9
0.8
0.7
0.6 Ternary-Cursor
CH - IPA

0.5
0.4 Separatrix, 101.3 kPa, ALC_VLLE

PRO/II - Column T-2, Vapour
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
Note: Various PRO/II Tower Profiles can be imposed.

Data Container The Column data are saved to Sheet "CLMN"
Note: The tower simulation data need not necessarily be converged, thus
supporting debugging and analysis of unconverged simulation runs.
Hitting the control will open the PRO/II Stream Selection

Window.
Plot PRO/II
Streams
The Plot below shows the vapour overhead product of Column T-2 in
PRO/II Model Azeo_a3-splitter.prz. It also shows the decanter's
organic and aqueous products. In the context of the thermodynamic
behaviour the respective stream compositions are confirmed.
H2O-IPA-CH
1
0.9
0.8
0.7
Ternary-Cursor
CH - IPA

0.4 PRO/II - Column T-2, Vapour
PRO/II - Stream VAPOUR
PRO/II - Stream PHASE-H2O
PRO/II - Stream PHASE-CH
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
Note: PRO/II Tower Profiles can be imposed.

The Stream data are saved to Sheet "STRM"
Data Container
Workbook Group
The Workbook Group supports all user actions that relate to the
management of the Excel Workbook.
Use the control to open a new workbook session.

Open a new The new workbook session will be initialized based on the actual system
Workbook configuration. The configuration data for a workbook session are saved in
sheet "mngr".
Data Container
The actual workbook will remain available in the application background.

Use the Windows Toggle option if you wish to re-activate it.
Note: Any workbook can be saved, closed and reopened at a later point in time.
The user can continue working with the workbook without the need to specify
the PRO/II Database again. The PRO/II Database filename is saved to cell D1,
therefore it can be used to re-connect later. See also Chapter Select PRO/II
Database.
Use the control to open a the Remove Series Window.

Remove Curve
Series from
Worksheets, Chart
and Legend

Use the dropdown to select the name of the worksheet you would like to
clear out. Currently, all data of a worksheet will be cleared, ie. not
individual curves.
After selecting an entry in the dropdown hit Delete. As a result, all curves
and legend entries that correspond to the specified worksheet disappear
from the graph. Also, the selected worksheet is reset to its initial state
(maintaining the formats).
Data Container Note: As a result, the corresponding entry in column F in worksheet
"mngr" is reset to 3. This value indicates the last numeric entry in a
worksheet .When generating new curve data this value is always adjusted
to the last numeric value.
The VLLE-Plotbar Management Group supports all user actions that relate
to the management of the VLLE-Plotbar.
Use the control to collapse the large VLLE-Plot toolbar.
Collapse the
Once collapsed, the control changes to .
VLLE-Plot toolbar
Use the control to remove the VLLE-Plot toolbar.
Remove the VLLE- In order to bring it back, the user must follow the instructions at the
Plot toolbar beginning of this manual in section Initializing.
The VLLE Ternary Cursor Commandbar
The Ternary Cursor Commandbar supports the analysis of a ternary

mixture using point flashes. The commandbar allows to define the stepsize
o the Ternary Cursor, to swap the binary pair along their axis, the
plotstyle. Most importantly, it allows to generate point flashes and point
residue curves at the location of the Ternary Cursor.
Importantly, it allows to generate point flashes and point residue curves at


The Ternary Cursor Group supports all user actions that relate to the
Ternary Cursor and curves generated at its actual location.
If Chart "2D" is active, the control allows to move the Ternary Cursor
Movement upwards.
direction of the
ternary cursor in
the upward If Chart "3D" is active, the control allows to rotate the Surface Plot
direction
upwards.
Movement downwards.
direction of the
ternary cursor in
If Chart "3D" is active, the control allows to rotate the Surface Plot
the downward
direction
downwards.
Movement leftwards.
direction of the
ternary cursor in If Chart "3D" is active, the control allows to rotate the Surface Plot
the leftward
direction leftwards.
Movement rightwards.
direction of the
ternary cursor in
the rightward
direction rightwards.
Using the control allows to specify the stepsize for movements

of the Ternary Cursor. The numbers refer to molar fractions.
Specify the
Stepsize of the
Ternary Cursor

The options are shown below.
The picture below indicates the directions the Ternary Cursor can be moved
in order to access a desired composition.
The coordinates of the Ternary Cursor are saved on sheet "Flash". The blue
Data Container numbers in line 3 , columns E, F and G hold the molar fraction. This fraction is
plotted in sheet "2D" by a red circle.
Note: It is also possible to manually enter the compositions of the Ternary Cursor
directly into cells E3 and F3. Note that cell G3 has the formula "=1.0-E3+F3".
Hence, only E3 and F3 must be entered.
Swap Binary Pair Group
The Swap Binary Pair Group allows to swap the component assignments
of the binary pairs. This results in a rearrangement of the plots
The control allows to swap the binary pair located on the diagonal
Swap the pair axis.
along the diagonal
Axis

The control allows to swap the binary pair located on the vertical axis
Swap the pair
along the vertical
Axis
The control allows to swap the binary pair located on the horizontal
axis
Swap the pair
along the
horizontal Axis
Plot Style Group
The Plot Style Group supports all user actions that relate to the Ternary
Cursor and curves generated at its actual location.
Using the dropdown allows to specify the color of Point-Flash

lines and Residue Curves.
Specify the Color
of Point-Flash
lines and Residue
Curves

The options are shown below.
H2O-IPA-CH
1
0.9
0.8
0.7
CH - IPA 0.6
0.5 Ternary-Cursor
Bubblepoint FlashFlash, 100 kPa, ALC_VLLE
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
The Chart above shows the tielines at the location of the Ternary Cursor
at 100 kPa (green) and at 500 kPa (red). The change in slope is obvious
and well documented through color and legend.
Using the dropdown allows to specify the symbol style of point

flash lines.
Specify the
Symbol Style of The options are shown below:
point flash curves
Using the dropdown allows to specify whether curves are

added to the legend or not.
Specify whether
Curves are Added The options are shown below:
to the Legend or
not
Residue Curve Group
The Residue Curve Group supports all user actions that relate to Point
Residue Curves. The term Point Residue Curves relates to residue curves

that are initialized by means of the Ternary Cursor. This distinction helps
to tell it from the curve mechanism by means of the grid function.
Hitting the control launches the calculation of a "Point-

Residue Curve" at the location of the Ternary Cursor.
Generate a Point-
Residue Curve
H2O-IPA-CH
1
0.9
0.8
0.7
0.6
CH - IPA
0.5
Ternary-Cursor
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
The diagram shows a Residue curve at at the location of the Ternary Cursor.
Point Flash Group
The Point Flash Group supports all user actions that relate to Point
Flashes. The term Point Flashes relates to flashes that are initialized by
means of the Ternary Cursor. This distinction helps to tell it from any
other flashes called automatically by means of the various functions.
Hitting the control launches the calculation of a "Point-Flash" at

Perform a single
Point-Flash at the The user has various options to specify the Flash Type, be it isothermal,
location of the dew- or bubble-point. This is controlled through the dropdown
Ternary Cursor
element.
Data Container The latest numerical data for the flash are saved to Sheet "Flash".

The picture above shows a FixT type Point-Flash at 63.4C with the
composition according to cells E3, F3 and G3 with represent H2O, IPA
and CH respectively.
Note: Performing Point-Flashes in combination with option is a way to

avoid overloading the diagram with too many datapoints.
Note: Please be careful when working with the option as it

automatically changes the mixture composition in cells E3, F3 and G3.
Data Container All Point Flash results are saved in worksheet "FLSH"
Using the dropdown allows to specify the Flash-Type, ie.

Whether a bubblepoint, a dewpoint or a fixed temperature flash must be
Specify the Colour performed
of Point-Flash
lines and Residue The options are shown below.
Curves
The option reports temperature at bubble-point and vapor

composition that is in equilibrium with the (liquid) Ternary Cursor
composition.

The option reports temperature at dew-point and liquid-
composition that is in equilibrium with the (vapor) Ternary Cursor
composition.
On sheet "Flash", depending on the flash-type the numbers in Cells C3
and D3 behave as follows:
Bubblepoint, Dewpoint
o Pressure value in cell C3 serves as specification
o Temperature value in cell D3 serves as estimate
Fixed Temperature
o Temperature value in cell D3 serves as specification
Using the dropdown allows to specify the modus of Point-

Flashes. This works in combination with the function.
Specify the
modus of Point- The options are shown below.
Flashes
This control element is only enabled for in combination with or

flashes. The control-element is disabled. if flash-type is
selected.
In Progressive mode and in combination with the option, the
resulting vapor composition will automatically be passed to the Ternary
Cursor after the flash calculation. The user will see the Ternary Cursor
move to the vapor composition.
In Progressive mode and in combination with the option, the

resulting liquid composition will be passed to the Ternary Cursor after the
flash calculation. The user will see the Ternary Cursor move to the liquid
composition.

Use Single to devoke this modus,
H2O-IPA-CH
1
0.9
0.8
0.7
0.6 Ternary-Cursor
Flash, 101.3 kPa, ALC_VLLE
CH - IPA
0.5

0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
A typical chart after performing Point-Flashes is shown

above. It indicates how a composition that originally started in vapour-
liquid region moves into the heterogeneous region where it finally
approaches the ternary azeotrope. Five Point-Flashes have
been performed with the option invoked.
1
CLFR-MEOH-ACETONE
PRO/II Thermo Set = NRTL01 Pressure = 1.013 bar
0.9
0.8
0.7
ACETONE - MEOH
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
ACETONE - CLFR
The chart above shows how Point-Flashes were used to detail

the region next to the assumed saddle point, indicated by the Ternary
Cursor, here shown in dark blue.
Note: Progressive Flashes indicate in an interactive way where a composition
moves to after performing successive flashes.
Using the dropdown allows to specify whether a Point-Flash is

just calculated or also plotted.
Specify whether a
Point-Flash is just The options are shown below.
calculated or also
plotted

Note: Using Calculation Only allows to interactively request Point-flashes
without overloading the chart by adding too many points.
Using the entry field allows to specify the system temperature.

Specify System- This is only enabled if flash-type has been requested.
Temperature for
Fixed If or has been requested, this entry field is not enabled
Temperature for user-entries. In those cases the control element serves as a temperature
Point-Flashes indicator. It reports the temperatures of the last conducted point flash such
as .
Note: Each time a new temperature value is entered it is passed to sheet "Flash",
cell D3. When performing flashes, the internal subroutine will retrieve the
temperature value from this cell.
The Ternary Cursor Hide/Show Group
The Ternary Cursor Management Group supports all user actions that relate
to managing the Ternary Cursor. The Ternary Cursor can be hidden and
shown on the diagram.
Hitting the control removes the Ternary Cursor from the

diagram.
Hide / Show the
Ternary Cursor
Note: Hiding the Ternary Cursor may often be desireable when printing the
diagram.
After hitting the control the button caption turns to

and allows to bring the Ternary Cursor back into the chart.
Office 2007
The VLLE-Plot functions

The VLLE-Plot Main Command bar

Symbol Description
PRO/II File Group
define system
Select the mixture components
Select thermodynamic system
Specify system pressure. Unit of

measure is bound to kPa.
Plot a 3d-boiling surface.
Plot binary VLLE. This covers bubble

and dewpoint lines of each of the
existing binary system pairs that can
be composed.
Configure and generate a ternary

system plot including azeotropes,
Residue curves, boundary distillation
curves, tielines and binodal curve.
Specify starting points for multiple

Residue Curves, be they distributed
parallel the binary axes or close to
existing azeotropes resulting in
boundary distillation curves.
PRO/II Results Group

Plot column profiles of towers
available in PRO/II model
Plot streams available in PRO/II

model
Workbook Group
Open a new Workbook
Clear the contents of worksheets and

remove the respective curves and
legend entries from the diagram.
Collapses/expands the toolbar

toggling to
Remove the toolbar from Excel
The VLLE-Plot Ternary Cursor Commandbar
Ternary Cursor
Group
Movement direction of
ternary cursor
Specify stepsize for

movements of the
Ternary Cursor. The
numbers refer to
molar fractions.
Swap Binary Group
Swaps the binary pair

located on the diagonal
axis

located on the vertical
axis

located on the horizontal
axis
Ternary Cursor
Action Group
Specify the color of point

flash and residual curves.
Specify the symbol

style of point flash
curves
Specify whether curves

are added to the legend
or not.
Residue Curve Group
Generate a Point-
Residue Curve at the
location of the Ternary
Cursor.
Point Flash Group

Performa single Point-
Flash at the location of
the Ternary Cursor
Specify the Flash-Type,

ie. Whether a
bubblepoint, a dewpoint
or a fixed temperature
flash must be
performed.
Specify the modus of

Point-Flashes. In
Progressive mode the
resulting vapour or
liquid composition (this
depends of flash-type)
will be passed to the
Ternary Cursor. Use
Single to devoke this
modus,
Specify whether a
Point-Flash is just
calculated or also
plotted.
Specify System-
Temperature for
Fixed Temperature
Point-Flashes . This is
only enabled for
Fixed Temperature-
Flashes. Otherwise it
serves as temperature
indicator.

Hide/Show Ternary
Cursor Group
Hide/Show the Ternary

toggling to Cursor from the chart
Detailed Descriptions
VLLE-Plot Main Bar
The VLLE-Plot Main Bar supports the generation of binary and ternary
diagrams that display ternary mixture Vapour-Liquid-Liquid Equilibria
(VLLE) data. This includes
ternary boiling surface
plot binary boiling- and dewpoint curves
azeotropes
residue curves
tielines and binodal curve
It also allows access to PRO/II simulation results, ie.
PRO/II column profiles
stream compositions
Finally, in order to better manage the toolbar, which becomes part of the
Excel-Toolbar set, it allows
Toolbar and Worksheeet management
PRO/II Database Group
The PRO/II Database Group supports all user actions that relate to
specifying a PRO/II database file with the proper thermodynamical data,
be it components and thermodynamic sets.
Hitting the control will open the PRO/II File Window.

Select PRO/II
Database

After browsing for the PRO/II Database file, hit Connect.
Note: The PRO/II file serves as the container for components, thermodynamic
sets, columns and streams.
! Please ensure that in deg Celsius and Bar are selected as units of measure
The user may intend to add new VLLE data onto a ternary diagram that had been
generated earlier by using the VLLE Ternary Plot feature. In this case, the respective
workbook would need to be loaded into Excel, first. Hitting , the
PRO/II File window will now look slightly different. Having detected that a workbook
already exists, the window will allow to simply connect to the respective PRO/II file that
had been specified when the workbook had been initialized.
This feature allows the user to continue working with existing ternary diagrams.
The System Definition Group supports all user actions that relate to
specifying the system be it components, the thermodynamic method and
the system pressure.
Note: Currently all VLLE-calculations are performed at constant pressure
Hitting the control will open the System Definition Window.

Select the mixture
components

The components available in the connected PRO/II Database will show in
the dropdowns.
The dropdown controls are positioned according to the component
locations on the ternary plot.
After closing this window, all control elements in the VLLE-Plot toolbar
become enabled.
Note: The user can always change the components to superimpose ternary maps.
This is a powerful way to compare alternative candidates for entrainers.
Currently, the number of components is fixed to three.
Note: The macro has inbuilt functionality to support quaternary systems. This
feature is currently not available.
Acting on the control will display the thermodynamic sets

available in the PRO/II Database.
Specify the
system The options include all thermodynamic sets available in the connected
thermodynamic PRO/II Database file, e.g.
set
Note: The user can always change the thermodynamic set to superimpose ternary
maps. This is a powerful way to compare alternative thermodynamic sets, such as
sets with alternative binary interaction parameters, or alternative configurations
with respect to the methods.
Note: Each time a Thermo-Set is is selected it is passed to sheet "mngr", cell

A1. When performing flashes, the internal subroutine will retrieve the
thermo-set from this cell.

The control allows to enter and specify the system
pressure.
Specify the
system pressure Note: The user can always change the system pressure to superimpose ternary
maps. This is a powerful way to compare alternative system pressures.
Note: Each time a new pressure value is entered it is passed to sheet "Flash",
cell C3. When performing flashes, the internal subroutine will retrieve the
pressure specification from this cell.
The Ternary Surface Plot Group supports all user actions that relate to 3d-
charts showing either the dewpoint plane or the boiling point plane.
Hitting the control will open the Boiling Surface Window.

Plot a 3d-boiling
surface
The No. of Grid-points entry allows to specify the number of flash-

calculations along each binary axis.
Bubble- and Dew-point surfaces can be specified.
A 3d-plot exhibiting the boiling surface will be generated in Chart "3D"
Use the controls at lower right section of the chart to rotate the plot.

Note: The surface map allows an intuitive overview on the system. It quickly
The above plots show the bubble- and dewpoint planes for the system
H2O-IPA-CH at 101.3 kPa using a grid of 52 datapoints.
While the bubble-point surface (left) indicates the LLE-region, the
dewpoint surface (right) indicates the location of the ternary azeotrope.
Numerical data are located in Sheets "t_1" and "t_2".
Data Container Sheet t_1:

Data Container Sheet t-2:
The Binary VLLE Plot Group supports all user actions that relate to binary
VLLE-plots showing both the dewpoint curve and the boiling point curve.
Hitting the control will open the Binary VLLE Plots Window.
Binary VLLE
Plots Window
The No. of Points entry allows to specify the number of flash-calculations

along each binary axis.
A 2d-plot exhibiting bubble- and dewpoint curves for each of the binary
pairs will be generated in Chart "TXY"

H2O-IPA-CH
PRO/II Binary BVLE
157.01 157.01
145.45 145.45
133.90 133.90
H2O-IPA Boilingpoints 101.3 kPa ALC_VLLE

122.34 122.34 H2O-IPA Dewpoints 101.3 kPa ALC_VLLE
Temperature [C]
H2O-CH Boilingpoints 101.3 kPa ALC_VLLE
H2O-CH Dewpoints 101.3 kPa ALC_VLLE
IPA-CH Boilingpoints 101.3 kPa ALC_VLLE
110.78 110.78 IPA-CH Dewpoints 101.3 kPa ALC_VLLE
H2O-IPA Boilingpoints 500 kPa ALC_VLLE
H2O-IPA Dewpoints 500 kPa ALC_VLLE
H2O-CH Boilingpoints 500 kPa ALC_VLLE
99.23 99.23 H2O-CH Dewpoints 500 kPa ALC_VLLE
IPA-CH Boilingpoints 500 kPa ALC_VLLE
IPA-CH Dewpoints 500 kPa ALC_VLLE
Reihe1
87.67 87.67
76.11 76.11
64.56 64.56
53.00 53.00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x [-]
The chart above shows bubble and dewpoint curves for the three available
binary pairs of the system H2O, IPA and CH. The curves were requested
at 101.3 kPa and 500 kPa using the "Append" option. It can be seen how
the H2O-CH Azeotrope (blue lines) moves to the right at the higher
pressure while the IPA-CH Azeotrope (red lines) moves to the left.
Note: The binary curves allow an intuitive overview on the system. It quickly
Data Container Numerical data are located in Sheet "BVLE"

The Ternary VLLE Plot Group supports all user actions that relate to
ternary diagrams showing azeotropes, tielines and Residue Curves.
Hitting the control will open the Ternary Plot Window.

Create a Ternary
Chart
This window is composed of four main sections:

Integration Settings for Residue Curves
Integration Settings for Azeotropes

Integration Setting for Tielines and Binodal Curve
Configuration of the Plot
A typical Ternary Plot exhibiting binary and ternary azeotropes, tielines

and binodal curve is shown below. This plot was produced using the
default settings and by configuring the plot as shown in the Plot-Options
box.
H2O-IPA-CH
1
0.9
0.8
0.7
0.6
CH - IPA
Ternary-Cursor
0.5
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
Note: To compute Residue curves, the user is advised to generate starting points
for Residue curves first. Use the button , which is explained in next
chapter.
Isothermal Tielines
Option Depending on the settings in the LLE Settings tieleines are generated at the
bubblepoint or, alternatively, at isothermal conditions. For isothermal
tielines, the user must activate the Isothermal Radio-Button. A
Temperature entry box appears for the specification of the temperature.

The plot is generated in Charz "2D"
The numerical data are stored in sheets
Sheet "AZP"
o Azeotropic points
Data Container
Sheet "LLE"
o Tielines and binodal curve
Data Container
Sheet "RC"
o Residue curves
Data Container

Technical Technical Reference
References Azeotropes Settings
Azeotropes are calculated iteratively by minimizing the expression

(1) y-x
for all three components in the ternary system.

Technical Reference
Azeotropes Settings:
Azeotropes Label Description Range good value
Max. Iter. : The maximum number of iterations for the 0<i<inf 100
minimization
Tolerance : An internal tolerance 0<tol<1 .0001
Technical Reference
Residue Curve Settings
Residue Curves are calculated by using eq. 15 in Doherty, Perkins, On

the Dynamics of Distillation Processes-I, page 283, Chem. Eng. Science,
1978, vol 33 pp281-301.
The equation results in:
(1) d_x/d_ksi= x -y
(2) x_new=x_old + (x_old-y_old)*ksi
where x_new and x_old are two successive points of the curve, x_new being
calculated as a function of the old x and y and the integration constant ksi.
x and y are molefractions of the mixture.
Enter the settings for the numerical calculations in the Integration
Settings entry-group.
Integration Settings:
ksi : its the integration constant ksi in eq. (2) 0<ksi<1 0.4
Note: ksi=1 will result in Distillation Curve
Calculations instead of Residue Curves Calcs. In
case of binaries these would be McCabe Thiele
100% Steps between bubble- and dew-curve. Here
it would be 100% steps between bubble- and dew-
plane. For narrow boiling systems ksi=1 is ok. In
other cases make ksi smaller than lets say 0.3.
ksi-min : Although you fix the value for ksi, ksi would get 0<ksi<1 0.005
reduced artificially by the calculation engine
whenever the ksi-value results in negative
compositions. The entry for ksi-min marks the
minimum value the integration constant ksi in eq.
(2) would get assigned by the calculation engine.
Min. Iter. : The minimum number of points to be calculated for 0<i<inf 10

each residue curve.

Max. Iter. : The maximum number of points to be calculated for min. It<i<inf 50
each residue curve
Tolerance : If the difference between x_new and x_old gets 0<tol<1 .0001
smaller than Tolerance, calculations are stopped.
This normally marks an azeotrope or a pure
component corner.
2. In order to calculate residue-curves you must define a grid of

starting points, first.. Use the control to do that.

Perturbing Azeotropes Perturbing binary Azeotropic
Perturbance of Perturbing binary Azeotropic compositions delivers 0<pert<1 1e-4
Azeotrope new ternary compositions which, if you route a
residue curve through this point, behave similar
though not necessarily exactly like boundary
residue curves. The azeotropic composition is
perturbed by the molar fraction of the third
component according the entry field, i.e. this value
is used as molefrac of the third component.
Note: Specifying small values for perturbance
serves as a first approach to approximate
boundary residue curves.
In order to calculate residue-curves that pass through perturbed binary

azeotropes, you must have to define these points, first. Use the
control to do that.

LLE Tielines and LLE-Settings
Binodal Curve
LLE-Calculations generate the tielines and the binodal curve.
The calculations consist of repeated two-liquid-phase flashes. Flash
compositions are always calculated as function of a given tieliene's length
and its midpoint, using the formula:
(5) x_new=x_midpoint + orthogonal step
(6) orthogonal step = percentage of the tieline-length
This is repeated until x_new lies outside the two-phase region.

LLE-Settings:
Max. Number The maximum number of tielines to be calculated 0<i<inf 50
th
Display Show only every i tieline o<=i<infinite 5
Frequency
% orthogonal Percentage of the tieline length at which the next 0< 5
steps composition point will be located orthogonally from perc<100
the momentary composition point.

The Residue Curve Management Group supports all user actions that
relate to the generation of starting points for Residue Curves.
Hitting the control will open the Residue Curve Starting Points
Specify starting Window.
points for multiple
Residue Curves
The user has two options:

a) Hit Add Grid in order to distribute starting points (specify the no.)
parallel to the binary axes (specify distance). This option prepares the
generation of a geometrically build up residue curve map.
0.9
0.8
0.7
0.6
Ternary-Cursor
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Note: The red starting points will disappear after the Residue Curves have been
calculated.
b) Hit Perturb Azeotropes in order to position starting points right next to
existing binary azeotropes. This option prepares the generation of residue
curves that come very close to boundary distillation curves. The amount of
perturbation of the binary mixture into the ternary region is according to
the value specified in . An exact mathematical procedure for
detecting the location of boundary curves, involves a deeper analysis
Note: The blue line is only temporary and has no thermodynamic meaning. This
line and also the blue starting points will disappear after the boundary
distillation curves have been calculated.

After generating the starting points use either or in
order to generate the Residue curves. The resulting maps for GRID and Perturb
Azeotropes A
H2O-IPA-CH H2O-IPA-CH
1 1
PRO/II Ternary Calculations PRO/II Ternary Calculations
0.9 0.9
0.8 0.8
0.7 0.7
0.6 0.6
Ternary-Cursor
CH - IPA
CH - IPA
Ternary-Cursor
0.4 Binodal Curve, 101.3 kPa, ALC_VLLE 0.4 Separatrix, 101.3 kPa, ALC_VLLE
0.3 0.3
0.2 0.2
0.1 0.1
0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O CH - H2O
Data Container The generated Starting points are saved on sheet "GRID"
PRO/II Model Results Group
The PRO/II Model Results Group supports all user actions that relate to
retrieving simulation model data from connected PRO/II models.
Note: This powerful feature enables the engineer to review his model results
within the thermodynamic context. It allows him or her to gain full control on the
simulation model results.
Hitting the control will open the PRO/II Column Selection

Window.
Plot PRO/II
Column Profiles
The Plot below shows the Vapour profile of Column T-2 in PRO/II Model
Azeo_a3-splitter.prz. It is clearly indicated that the overhead vapour

product is close to the ternary azeotrope, while the bottom (vapour)
composition is almost pure IPA.
The fact that the profile slightly crosses the boundary distillation curve is
explained by slightly different pressures in tower operation and Residue
curve map.
H2O-IPA-CH
1
0.9
0.8
0.7
0.6 Ternary-Cursor
CH - IPA

0.5
0.4 Separatrix, 101.3 kPa, ALC_VLLE

PRO/II - Column T-2, Vapour
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
Note: Various PRO/II Tower Profiles can be imposed.

Data Container The Column data are saved to Sheet "CLMN"
Note: The tower simulation data need not necessarily be converged, thus
supporting debugging and analysis of unconverged simulation runs.
Hitting the control will open the PRO/II Stream Selection

Window.
Plot PRO/II
Streams

The Plot below shows the vapour overhead product of Column T-2 in
PRO/II Model Azeo_a3-splitter.prz. It also shows the decanter's
organic and aqueous products. In the context of the thermodynamic
behaviour the respective stream compositions are confirmed.
H2O-IPA-CH
1
0.9
0.8
0.7
Ternary-Cursor
CH - IPA

0.4 PRO/II - Column T-2, Vapour
PRO/II - Stream VAPOUR
PRO/II - Stream PHASE-H2O
PRO/II - Stream PHASE-CH
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
Note: PRO/II Tower Profiles can be imposed.

The Stream data are saved to Sheet "STRM"
Data Container
Workbook Group
The Workbook Group supports all user actions that relate to the
management of the Excel Workbook.

Use the control to open a new workbook session.
Open a new The new workbook session will be initialized based on the actual system
Workbook configuration. The configuration data for a workbook session are saved in
sheet "mngr".
Data Container
The actual workbook will remain available in the application background.

Use the Windows Toggle option if you wish to re-activate it.
Note: Any workbook can be saved, closed and reopened at a later point in time.
The user can continue working with the workbook without the need to specify
the PRO/II Database again. The PRO/II Database filename is saved to cell D1,
therefore it can be used to re-connect later. See also Chapter Select PRO/II
Database.
Use the control to open a the Remove Series Window.
Remove Curve
Series from
Worksheets, Chart
and Legend
Use the dropdown to select the name of the worksheet you would like to
clear out. Currently, all data of a worksheet will be cleared, ie. not
individual curves.
After selecting an entry in the dropdown hit Delete. As a result, all curves
and legend entries that correspond to the specified worksheet disappear
from the graph. Also, the selected worksheet is reset to its initial state
(maintaining the formats).
Data Container Note: As a result, the corresponding entry in column F in worksheet
"mngr" is reset to 3. This value indicates the last numeric entry in a
worksheet .When generating new curve data this value is always adjusted
to the last numeric value.

The VLLE-Plotbar Management Group supports all user actions that relate
to the management of the VLLE-Plotbar.
Use the control to collapse the large VLLE-Plot toolbar.

Collapse the
VLLE-Plot toolbar Once collapsed, the control changes to .
Use the control to remove the VLLE-Plot toolbar.
Remove the VLLE- In order to bring it back, the user must follow the instructions at the
Plot toolbar beginning of this manual in section Initializing.
The VLLE Ternary Cursor Command bar
The Ternary Cursor Commandbar supports the analysis of a ternary

mixture using point flashes. The commandbar allows to define the stepsize
of the Ternary Cursor, to swap the binary pair along their axis, the
plotstyle. Most importantly, it allows to generate point flashes and point
residue curves at the location of the Ternary Cursor.
Importantly, it allows to generate point flashes and point residue curves at

The Ternary Cursor Group supports all user actions that relate to the
Ternary Cursor and curves generated at its actual location.
Movement If Chart "2D" is active, the control allows to move the Ternary Cursor
direction of the
ternary cursor in upwards.
the upward
direction
upwards.

Movement
direction of the downwards.
ternary cursor in
the downward If Chart "3D" is active, the control allows to rotate the Surface Plot
direction
downwards.
Movement leftwards.
direction of the
ternary cursor in
the leftward If Chart "3D" is active, the control allows to rotate the Surface Plot
direction
leftwards.
Movement rightwards.
direction of the
ternary cursor in If Chart "3D" is active, the control allows to rotate the Surface Plot
the rightward
direction rightwards.
Using the control allows to specify the stepsize for

movements of the Ternary Cursor. The numbers refer to molar fractions.
Specify the The options are shown below.
Stepsize of the
Ternary Cursor
The picture below indicates the directions the Ternary Cursor can be moved
in order to access a desired composition.

The coordinates of the Ternary Cursor are saved on sheet "Flash". The blue
Data Container
numbers in line 3 , columns E, F and G hold the molar fraction. This fraction is
plotted in sheet "2D" by a red circle.
Note: It is also possible to manually enter the compositions of the Ternary Cursor
directly into cells E3 and F3. Note that cell G3 has the formula "=1.0-E3+F3".
Hence, only E3 and F3 must be entered.
Swap Binary Pair Group
The Swap Binary Pair Group allows to swap the component assignments
of the binary pairs. This results in a rearrangement of the plots
Swap the pair The control allows to swap the binary pair located on the diagonal
along the diagonal
Axis axis
The control allows to swap the binary pair located on the vertical axis
Swap the pair
along the vertical
Axis

Swap the pair The control allows to swap the binary pair located on the horizontal
along the axis
horizontal Axis
Plot Style Group
The Plot Style Group supports all user actions that relate to the Ternary
Cursor and curves generated at its actual location.
Using the dropdown allows to specify the color of Point-

Flash lines and Residue Curves.
Specify the Colour
of Point-Flash The options are shown below.
lines and Residue
Curves

H2O-IPA-CH
1
0.9
0.8
0.7
0.6
CH - IPA
0.5 Ternary-Cursor
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
The Chart above shows the tielines at the location of the Ternary Cursor
at 100 kPa (green) and at 500 kPa (red). The change in slope is obvious
and well documented through color and legend.
Using the dropdown allows to specify the symbol style of

point flash lines.
Specify the
Symbol Style of The options are shown below:
point flash curves
Using the dropdown allows to specify whether curves are

added to the legend or not.
Specify whether
Curves are Added The options are shown below:
to the Legend or
not
Residue Curve Group
The Residue Curve Group supports all user actions that relate to Point
Residue Curves. The term Point Residue Curves relates to residue curves
that are initialized by means of the Ternary Cursor. This distinction helps
to tell it from the curve mechanism by means of the grid function.
Hitting the control launches the calculation of a "Point-

Residue Curve" at the location of the Ternary Cursor.
Generate a Point-
Residue Curve

H2O-IPA-CH
1
0.9
0.8
0.7
0.6
CH - IPA
0.5
Ternary-Cursor
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
The diagram shows a Residue curve at the location of the Ternary Cursor.
Point Flash Group
The Point Flash Group supports all user actions that relate to Point
Flashes. The term Point Flashes relates to flashes that are initialized by
means of the Ternary Cursor. This distinction helps to tell it from any
other flashes called automatically by means of the various functions.
Hitting the control launches the calculation of a "Point-Flash" at the

location of the Ternary Cursor.
Perform a single
Point-Flash at the The user has various options to specify the Flash Type, be it isothermal,
location of the dew- or bubble-point. This is controlled through the
Ternary Cursor dropdown element.
The latest numerical data for the flash are saved to Sheet "Flash".
Data Container

The picture above shows a FixT type Point-Flash at 63.4C with the
composition according to cells E3, F3 and G3 with represent H2O, IPA
and CH respectively.
Note: Performing Point-Flashes in combination with option is a

way to avoid overloading the diagram with too many datapoints.
Note: Please be careful when working with the option as it

automatically changes the mixture composition in cells E3, F3 and G3.
Data Container All Point Flash results are saved in worksheet "FLSH"
Using the dropdown allows to specify the Flash-Type, ie.

Whether a bubblepoint, a dewpoint or a fixed temperature flash must be
Specify the Colour
performed
of Point-Flash
lines and Residue The options are shown below.
Curves
The option reports temperature at bubble-point and vapor

composition that is in equilibrium with the (liquid) Ternary Cursor
composition.
The option reports temperature at dew-point and liquid-

composition that is in equilibrium with the (vapor) Ternary Cursor
composition.
On sheet "Flash", depending on the flash-type the numbers in Cells C3
and D3 behave as follows:
Bubblepoint, Dewpoint
o Temperature value in cell D3 serves as estimate

Fixed Temperature
o Temperature value in cell D3 serves as specification
Using the dropdown allows to specify the modus of Point-

Specify the Flashes. This works in combination with the function.
modus of Point- The options are shown below.
Flashes
This control element is only enabled for in combination with

or flashes. The control-element is disabled.
if flash-type is selected.
In Progressive mode and in combination with the option,

the resulting vapor composition will automatically be passed to the
Ternary Cursor after the flash calculation. The user will see the Ternary
Cursor move to the vapor composition.
In Progressive mode and in combination with the option,

the resulting liquid composition will be passed to the Ternary Cursor after
the flash calculation. The user will see the Ternary Cursor move to the
liquid composition.
Use Single to devoke this modus,
H2O-IPA-CH
1
0.9
0.8
0.7
0.6 Ternary-Cursor
CH - IPA

0.5

0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
CH - H2O
A typical chart after performing Point-Flashes is shown

above. It indicates how a composition that originally started in vapour-
liquid region moves into the heterogeneous region where it finally
approaches the ternary azeotrope. Five Point-Flashes have
been performed with the option invoked.

1
CLFR-MEOH-ACETONE
PRO/II Thermo Set = NRTL01 Pressure = 1.013 bar
0.9
0.8
0.7
ACETONE - MEOH
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
ACETONE - CLFR
The chart above shows how Point-Flashes were used to

detail the region next to the assumed saddle point, indicated by the
Ternary Cursor, here shown in dark blue.
Note: Progressive Flashes indicate in an interactive way where a composition
moves to after performing successive flashes.
Using the dropdown allows to specify whether a Point-

Flash is just calculated or also plotted.
Specify whether a
Point-Flash is just The options are shown below.
calculated or also
plotted
Note: Using Calculation Only allows to interactively request Point-flashes

without overloading the chart by adding too many points.
Using the entry field allows to specify the system

Specify System- temperature. This is only enabled if flash-type has been
Temperature for requested.
Fixed
Temperature If or has been requested, this entry field is
Point-Flashes not enabled for user-entries. In those cases the control element serves as a
temperature indicator. It reports the temperatures of the last conducted
point flash such as .
Note: Each time a new temperature value is entered it is passed to sheet "Flash",
cell D3. When performing flashes, the internal subroutine will retrieve the
temperature value from this cell.

The Ternary Cursor Hide/Show Group
The Ternary Cursor Management Group supports all user actions that relate
to managing the Ternary Cursor. The Ternary Cursor can be hidden and
shown on the diagram.
Hitting the control removes the Ternary Cursor from the

diagram.
Hide / Show the
Ternary Cursor Note: Hiding the Ternary Cursor may often be desirable when printing the
diagram.
After hitting the control the button caption turns to

and allows to bring the Ternary Cursor back into the chart.

Invensys Systems, Inc.
26561 Rancho Parkway South
Lake Forest, CA 92630
United States of America
http://iom.invensys.com
Global Customer Support

Inside U.S.: 1-866-746-6477
Outside U.S.: 1-508-549-2424 or contact your
local Invensys Representative.
Email: Invensys.iom.support@Schneider-electric.com
Website: http://support.ips.invensys.com

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Invensys Systems, Inc.

Initializing Office 2003 ...................................................................................... 1

Initializing Office 2007 ...................................................................................... 2

Open Issues ............................................................................................................ 4

OFFICE 2003 ................................................................................................................... 5

THE VLLE-PLOT FUNCTIONS................................................................................... 5

The VLLE-Plot Main Commandbar ...................................................................... 5

The VLLE-Plot Ternary Cursor Commandbar ...................................................... 7

DETAILED DESCRIPTIONS ..............................................................................................10

VLLE-Plot Main Bar .................................................................................................10

PRO/II Database Group ........................................................................................10

Select PRO/II Database .....................................................................................10

System Definition Group ......................................................................................11

Select the mixture components .........................................................................11

Specify the system thermodynamic set .............................................................12

Specify the system pressure ..............................................................................12

Ternary Surface Plot Group ..................................................................................13

Plot a 3d-boiling surface ...................................................................................13

Binary VLLE Plots Window .............................................................................14

Ternary VLLE Plot Group ....................................................................................16

Create a Ternary Chart ......................................................................................16

Residue Curve Management Group ......................................................................21

PRO/II Model Results Group ................................................................................23

Plot PRO/II Column Profiles ............................................................................23

Plot PRO/II Streams ..........................................................................................24

Workbook Group ..................................................................................................25

Open a new Workbook .....................................................................................25

Remove Curve Series from Worksheets, Chart and Legend ............................25

VLLE-Plotbar Management Group.......................................................................26

Collapse the VLLE-Plot toolbar........................................................................26

Remove the VLLE-Plot toolbar ........................................................................26

The VLLE Ternary Cursor Commandbar .................................................................26

Ternary Cursor Group ...........................................................................................27

Movement direction of the ternary cursor in the upward direction ...................27

Movement direction of the ternary cursor in the downward direction ..............27

Movement direction of the ternary cursor in the leftward direction..................27

Movement direction of the ternary cursor in the rightward direction ...............27

Specify the Stepsize of the Ternary Cursor .......................................................27

Swap Binary Pair Group .......................................................................................28

Swap the pair along the diagonal Axis ..............................................................28

Swap the pair along the vertical Axis................................................................29

Swap the pair along the horizontal Axis ...........................................................29

Plot Style Group ....................................................................................................29

Specify the Color of Point-Flash lines and Residue Curves..............................29

Specify the Symbol Style of point flash curves ................................................30

Specify whether Curves are Added to the Legend or not ..................................30

Residue Curve Group ............................................................................................30

Generate a Point-Residue Curve .......................................................................31

Point Flash Group .................................................................................................31

Specify the Colour of Point-Flash lines and Residue Curves............................32

Specify the modus of Point-Flashes ..................................................................33

Specify whether a Point-Flash is just calculated or also plotted .......................34

Specify System-Temperature for Fixed Temperature Point-Flashes ................35

The Ternary Cursor Hide/Show Group .................................................................35

OFFICE 2007 ..................................................................................................................35

THE VLLE-PLOT FUNCTIONS..................................................................................35

The VLLE-Plot Main Command bar ....................................................................35

The VLLE-Plot Ternary Cursor Commandbar .....................................................37

DETAILED DESCRIPTIONS ..............................................................................................40

VLLE-Plot Main Bar .................................................................................................40

PRO/II Database Group ........................................................................................40

Select PRO/II Database .....................................................................................40