UniSim Design Tutorial CHEE 399

Queens University Department of Chemical Engineering

2008
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Introduction
UniSim (very similar to HYSYS) is a program used to design
chemical plants. It is built around:
a library of the physical properties of a large number of
chemical species
a set of subroutines to estimate the behavior of many types
of plant equipment (heat exchangers, reactors, etc.)
a graphical user interface to accept specifications for the
case, and display results
The user describes the process in terms of pieces of equipment
interconnected by process streams, and the program solves all
the mass/energy/equilibrium equations, taking into consideration
the specified design parameters for the units.

In this tutorial, you will be introduced to some of the basic

features of UniSim. Once you have completed this tutorial, it is
highly recommended that you attempt to work through the
advanced tutorial (available for download on the course
webpage), as it will introduce you to additional unit operations
and features. Upon completion of both tutorials, you will be
well-prepared to dig into the plant optimization assignments.

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Separating CO2 from Synthesis Gas

In this years Integrated Design Project, we are interested in
developing a process to obtain pure hydrogen (H2) from
Synthesis Gas (syngas) which, for the purposes of this
assignment, is a mixture of CO2, CO, H2 and H2O. The reaction
governing the ratio of these gasses is:
CO + H2O H2 + CO2
If we drive the reaction equilibrium towards the production of
H2, we will also increase ratio of CO2 in the gas mixture. This
CO2 is then can be removed from the syngas using Selexol, a
liquid absorbent. Since Selexol is a physical absorbent,
decreasing the temperature and increasing the pressure will drive
CO2 to dissolve into the liquid. Downstream, the CO2 can then
be removed by decreasing the pressure which will cause the
solvent to degas.
The amount of CO2 that the Selexol is capable of absorbing can
be calculated based on the principles of vapour/liquid
equilibrium (VLE). Since Selexol and CO2 are not chemically
similar, gas solubility cannot be accurately predicted using an
unmodified Raoults law (which would assume the fluids are
ideal). Our choice of property package will determine how the
model behaves when operating outside of conditions where
ideality holds. If we use the UNIQUAC (UNiversal QUAsi
Chemical) model, gas solubility can be calculated using a set of
binary coefficients. Experimental values for these binary
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coefficients are unavailable in the UniSim database. The

UNIFAC (UNiversal Functional Activity Coefficient) method
can be used to generate semi-theoretical estimates of these
binary coefficients based on molecular size and shape
differences and molecular interactions in the system. These
binary coefficients can then be validated by comparing the
solubilities predicted by the simulation to the manufacturers
data (refer to Genosorb_data.pdf use Genosorb 1753). If the
solubilities are not being predicted correctly, the binary
coefficients can be modified using an educated trial-and-error
basis.
We will develop a model capable of performing the solubility
calculation. The binary coefficients of the UNIQUAC model
will be adjusted to match the manufacturers solubility data.
These binary coefficients will then be input into the Integrated
Design Project process model.
The following diagram shows the process model we will use in
our solubility calculation for CO2 in Selexol.

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To ensure the Selexol is saturated with CO2, a stream containing

excess amounts of CO2 is mixed with a stream of pure Selexol.
This mixed stream will contain two phases: a liquid stream of
Selexol saturated with CO2, and a vapour stream consisting of
excess CO2. The excess CO2 (beyond saturation) is removed
using a (drum) separator, leaving us with the CO2-saturated
Selexol stream. A component splitter (aka a black box)
separates the CO2 from the Selexol, allowing us to read off the
normal volume of CO2 gas that was dissolved in the Selexol on a
per kg basis, just as it is reported in the manufacturers data file.
The binary coefficients can then be easily adjusted until the
model predictions match the experimental data.

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Setting up Data for the Model

Open UniSim (Accessed under Honeywell from the Start menu
in Windows).

Click on the New File icon

and get:

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Thermodynamics
Click on the Fluid Pkgs tab.

In UniSim, a Fluid Package includes all the thermodynamic,

component and reaction parameters required to run the model.
It is possible to have multiple packages in a model. For
example, in a more complex plant model, one could add more
than one fluid package if they wanted to use one particular
thermodynamics model for the reactors and a different
thermodynamics model for other unit operations.
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Click on Add and scroll to find UNIQUAC, since we are using

the UNIQUAC method to model the thermodynamics of our
system.

Note that default name of the package is Basis-1 and our

component materials will go into Components List - 1.
Adding Components
Close the Fluid Package window and click on the Components
tab of the Simulation Basis Manager window.

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Select Component List 1 and click on View.

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We will now add the four components of the Syngas mixture

(CO, H2O, H2, and CO2) to our components list. Lets begin
with CO by entering Carbon_Monoxide in the Match field.
Notice that if you forget the underscore ( _ ), the search will not
turn up any components!

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Click on Add Pure and do the same with Water.

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Often it is easier to search for and add compounds using their

chemical formulas. Select the Formula option and search for
H2. Add Hydrogen to the Selected Components list.

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Do the same thing with CO2.

The final component we will add is Selexol. Select the Full

Name / Synonym option and search for Selexol and add it to
the list of components.

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Close the components window. Now that we have finished

adding all of the components, it would be a good idea to save the
case. As with most Windows programs, this can be
accomplished by clicking on File Save. Save the file as
399tutor01.

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Estimating Binary Coefficients with UNIFAC

The UNIQUAC model requires a set of binary coefficients.
These can be estimated using the UNIFAC method. From the
Simulation Basis Manager window, click on the Fluid
Packages tab. Select Basis-1 and click on the View button.
Now, click on the Binary Coefficients tab to access the Activity
Model Interaction Parameters window.

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We are interested in the bottom row, the binary coefficients that

mathematically describe the interaction between the component
gasses when dissolving in Selexol.
Since the UNIFAC VLE option is automatically selected, click
on the Unknowns Only button to obtain estimates for binary
coefficients that are were not available in the database.

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Now close the Fluid Packages window. It is now time to exit

the Basis Manager and enter the Simulation Environment. To
proceed with building the process model, click on the Return to
Simulation Environment button. You can also click on the
button in the main toolbar.
A warning window will pop up. Click Ok.

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Building the Process Flow Diagram

Save your progress. If you make a mistake in your model,
particularly one which causes UniSim to crash at an inopportune
moment, it is always handy to have an earlier version of the
model saved so you can quickly return to a case that worked. If
you havent developed a habit of saving your work often, now is
a good time to do so! Do a Save followed by Save As
399tutor02.

This is the blank screen on which you will model the process by
building a Process Flow Diagram (PFD).
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The PFD operations palette, as shown on the left, should be

visible. If it is not, click on Flowsheet Pallette.
We will begin by defining creating two feed streams into the
system. Double click on the blue material stream icon
bring up an empty stream window.

to

Note that the properties are being estimated using the Basis-1
package.

We will begin with Selexol feed stream. Enter the following

data:
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 Steam Name = Selexol_In

Temperature = 25
Pressure = 100 kPa
Mass Flow = 1000 kg / h

To finish the stream definition, we need to specify

the composition. Click on Composition on the left side of the
window.

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Click on field next to Selexol and enter 1. A new window will

pop up. Click on the Normalize button.

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Now, click OK. Click on Conditions to go back to the

Conditions window.

The bar near the bottom will turn green (OK) to indicate that
the stream is now fully-defined. UniSim has calculated the
variables that you did not specify and they show up a black font.
From now on, you will only be able to change values that show
up in a blue font, not the black ones. Close the feed stream
window.
Now we will repeat the process to define the CO2 feed stream.
On the operations palette, double click on the blue material
stream icon
to bring up an empty stream window. Enter in
the following information:
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 Steam Name = CO2_IN

Temperature = 25
Pressure = 100 kPa
Mass Flow = 1000 kg / h

Click on Composition and click on the field next to CO2. Enter

in 1. The composition input window will open up.

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Click Normalize then OK to exit this window. Clicking on

Conditions we can see that this feed stream has now been
defined.

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As expected, CO2 at 25 and 100 kPa (1 bar) exists as a vapour,

as indicated by a Vapour / Phase Fraction equal to 1.0. We
are now done specifying the CO2 feed stream, so close the feed
stream window.

Now it is time to add a mixer to combine the two feed streams.

Double click on the mixer icon

in the operations palette.

In the Name field, specify Feed Mixer. Then click on

<<Stream>> in the Inlets list. You will be presented with a
list of acceptable steams. Select CO2_IN.

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Now we will input the second input stream. In the second

<<Stream>> line, select Selexol_IN.
UniSim informs us that we still need to specify a product stream.
It often pays to check the status bar at the bottom of the page
when you are stuck. Sometimes it can provide helpful hints and
remind you if youve forgotten to specify an important design
parameter.
Next, click on the box below Output and you will see that there
are no candidate streams. So enter the name Mixed Feed.

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The mixer has now been sufficiently specified. We have chosen

to accept the default operating parameters. Clicking on
Parameters (on the left), will bring up the following screen.

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Each type of operation will have a set of parameters that may be

adjusted. The parameters are usually specific to the type of
operation you are specifying. For example, pump efficiency is
one of the parameters that may be adjusted when you are
designing a pump. For (drum) separators, the parameters screen
allows you to specify the pressure drops at the both the inlet and
vapour outlet (by default they are set to zero).
For our mixer operator, there is only one parameter that can be
changed: the method by which the outlet pressure is calculated.
There are two options.
When Equalize All is selected, UniSim checks that all of the
inlet streams have the same pressure. If this is the case, the
outlet stream pressure is set to equal the pressure of the inlet
streams. If one (or more) of the inlet streams has a different
pressure, UniSim will display a warning, informing you that the
system is over-specified. This problem can be fixed by going
back and changing the pressure specification of the offending
inlet stream (making sure that all your inlet streams have the
same pressure).
When Set Outlet to Lowest Inlet is selected, UniSim sets the
pressure of the exit stream to equal the lowest inlet stream
pressure. When this option is selected, the inlet streams can
have different pressures. In a real plant, the inlet streams to a
mixer will have the same pressure, so avoid selecting this option
if you can.
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By default, the Equalize All radio button is selected and we

do not want to change this. Close the window and take a look
at the main screen.

All of the streams are dark blue, indicating that UniSim is

happy (that all the conditions required to fullly specify a
stream have been made, and that all resulting phsyical properties
have been calculated)
The Flash System

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Once the feed streams are mixed together, the Selexol will
become saturated with CO2 from the feed stream. The Mixed
Feed stream will consist of two phases: a liquid stream (Selexol
saturated with CO2) and a vapour stream (the CO2 left over after
the Selexol is saturated). We need a separator to isolate the two
phases.
Double click on the separator icon
on the operations palette.
This will bring up a screen where you can specify the separator
design.

Rename the unit by typing Separator into the Name box.

Attach the Mixed Feed stream by clicking on the box below
Inlets and selecting it. In the Vapour Outlet box, type Excess
CO2. In the Liquid Outlet box, type Saturated Selexol.
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Note that according to UniSim, the unit has been sufficiently

specified. We could, should we wish to, alter some of the
design specifications. If we wanted to specify a pressure drop
across the inlet and/or vapour outlet, we could click on
Parameters which would bring up the following screen:

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The numbers in both boxes are blue, indicating that we could

choose to specify pressure drops or specify other parameters.
However we will stick with the defaults.
Close the Separator window and do a Save followed by a
Save As 399tutor03. Your PFD should look similar to this
one.

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Double click on the Excess_CO2 stream. This will open up a

new window giving us information on the vapour outlet stream.

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Take a look at the mass flow rate. Assuming the stream is

essentially pure CO2, it appears that of the 1000 kg of CO2 that
we feed in per 1000 kg of Selexol, 2 kg of CO2 will absorb into
the Selexol. Click on Composition on the left side of the
window.

This confirms that the stream is essentially pure carbon dioxide.

Our model predicts that 1000 kg of Selexol will absorb 2 kg of
CO2 at 25 and 1 bar of pressure. However the manufacturers
specifications list gas solubility in terms of N cm3/g bar. Note
that N stands for normal and not Newton and refers to a
predefined set of temperature and pressure conditions. Since
weve chosen to operate at 1 bar (100 kPa), we can simplify the

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units to N cm3/g, but this information is still unavailable with the

model in its present form.
Splitting Components
To determine the normal volume of gas capable of absorbing
into a kg (or g) of Selexol, we must split the components of the
Saturated Selexol stream.
On the operation palette, double click on the component splitter
icon.

Change the name of the unit to Splitter and specify the input
and output streams as shown.

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Click on Splits and click on the box immediately to the right of

CO2.

Click on Set to 1.0000 to specify that the Absorbed CO2

stream will contain CO2 only. Set the remaining components to
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0.0 by clicking on each of the corresponding boxes and clicking

Set to 0.00000.

Click on the Worksheet tab near the bottom of the window.

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We must specify the split stream pressures of both streams to

100 kPa, as shown.

The component splitter has not been sufficiently specified, so

UniSim is unhappy. If we look at the message window near the
bottom of the main window, we can gain an clue as to which
information is missing.

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UniSim is telling us that the temperature of the Selexol_OUT

stream is unknown. Specifying the temperature of one of the
outlet streams might fix this problem. Since we need to measure
normal CO2 volume at 25 , set the temperature of the
Absorbed CO2 stream to 25 .

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The component splitter design has now been sufficiently

specified. Close the Splitter window. Your process stream
should now look similar to the one below:

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Click on the Absorbed CO2 stream.

We already knew the mass flowrate of CO2 was around 2 kg.

The Conditions window does not tell us what the normal
volumetric flow rate of the CO2 stream. Click on Properties to
bring up the properties window.

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It is empty, so we must specify which additional properties we

want UniSim to calculate. On the main menu bar, click on Tools
Preferences to bring up the Session Preferences window.

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Check the Activate Property Correlations (Standard, Black Oil,

Electrolyte) box.

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Click on the Variables tab near the bottom of the window. In

the Available Unit Sets box, click on SI and click on the Clone
button.

Rename the new unit set as you please (In the tutorial, it has
been renamed CHEE 399) and make sure it is selected. In the
Display Units box, scroll down until you find Std. Gas Flow.
Change the unit from STD_m3/h to Nm3/h as shown.

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Now that you have specified the use of a customized set of

variables where the Std. Gas Flow is reported in N m3/ h, click
on Save Preferences near the bottom of the window to save your
preferences.
Close the preferences window and click on the Absorbed CO2
stream on the PFD to open up the corresponding stream
properties window.

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Click on Properties and scroll down until you can read off the
Std. Gas Flow rate.

According to the model, a stream of Selexol flowing at 1000 kg

/ h is capable of absorbing the equivalent of 0.9953 N m3 / h of
CO2. In other words, the solubility of CO2 in Selexol is 0.9953
N cm3 according to our model. This is less than the
experimental solubility value supplied by the manufacturer (3.1
N cm3) so we will have to adjust the corresponding binary
coefficient until our process model prediction matches the
manufacturers data.
Adjusting the Binary Coefficients
Without closing the Absorbed CO2 properties window, click
on the PFD window and minimize it.
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Now would be a good time to save your work. Save the latest
version of your document as 399tutor04.
Click on the beaker icon
to exit the simulation environment
and re-enter the basis environment. If it isnt already selected,
click on the Fluid Pkgs tab and click the View button to edit
the fluid package.
Now, click on the Binary Coeffs tab to bring up the binary
coefficients window.
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The binary coefficient for CO2 in Selexol that was estimated

using the UNIFAC method must be adjusted to ensure that the
CO2 solubility predicted by the UniSim model matches the
solubility data provided by the manufacturer. The binary
coefficient that you will have to adjust has been circled above.
Since we do not know whether we need to increase or decrease
the binary coefficient, lets begin by changing it to 69.000 and
pressing Enter (or click on another box). A window will pop up
warning you that changing the binary coefficient will affect the
simulation results.

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Click Yes to continue.

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Notice that the font colour changes from red to blue. Without
closing the Fluid Packages click on the
icon to return to
the simulation environment.
The same warning window will pop up again.

Click Ok. A second window will pop up, asking you if you
want to remain in HOLDING mode when entering the
simulation environment. In HOLDING mode, the solver will
not be active and computed values will not be updated.

Since we want new values to be computed, will click No. If you

click Yes by mistake, click on the green traffic light icon
to
activate the solver. Sometimes you may want to deactivate the
solver (for example, if you want to change more than one
parameter without the solver recalculating everything after each
and every change); this can be done simply by clicking on the
red traffic light icon.
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The Absorbed CO2 window should still be open. Click on

Properties and scroll down to read off the Std. Gas Flow rate.

The simulation prediction is getting closer to the experimental

data! Return to the basis environment and try re-adjusting the
binary coefficient. Your find your results should be these:
Binary
Coefficient

Std Gas Flow (N

m3 / h)

69.676

1.00

69.000

1.97

68.000

5.52

68.500

3.29

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68.600

2.97

68.550

3.13

68.560

3.09

68.558

3.10

Now that we have determined the binary coefficient for CO2 in

Selexol it is time to repeat the process for CO and H2. Make
sure you record your binary coefficients on a separate sheet (or
notepad file in case, later on, you mistakingly change the value
later on or reset the binary coefficients. Restore the PFD
window and save your work.

Repeat the Process for H2

In the PFD window, left click on the mouse. While holding
down the left mouse button, drag a box across the PFD model as
shown below:

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Rather than respecifying the entire process from scratch, we can

copy the present model and create a duplicate. Press Ctrl-C to
copy the highlight model (or use File Copy). Press Ctrl-V to
paste a copy of the model onto the PFD. An outline of the new
diagram will appear. Position the outline near the bottom of the
window and left-click the mouse to place the copy.

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Our view is currently less than optimal, but we can position the
units by clicking PFD Auto Position All, as shown below.

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Your PFD should now look similar to the one below.

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Select the CO2_IN-2 feed stream on the lower model and

change the Stream Name to H2_IN. Click on Composition
and change the mole fraction of Hydrogen to 1.0. The
composition window will open up. Change the mole fraction of
CO2 to 0 and then click OK.

Close the window. Now, double click on the Excess CO2-2

stream and change its name to Excess H2. Double click on
the Absorbed CO2-2 stream and change its name to
Absorbed H2.
Now we must modify the component splitter because it is
currently set to create a pure stream of CO2 (It would be great if
UniSim could read our minds and carry out the correct
modifications on its own). Double click on the second
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component splitter Splitter-2 to open up the component

splitter window. Click on the Design tab, then select Splits.
Change the split fractions of the Absorbed_H2 stream to 1.0
Hydrogen and 0.0 CO2.

Close the splitter window and open up the information window

for the Absorbed H2 stream. If you have carried out all of the
changes properly, your numbers should match the ones shown
below.

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The predicted solubility 0.0248 is not far off from the

manufacturers data 0.03.

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As before, adjust the corresponding binary coefficient until your

simulations prediction matches the experimental data. Record
your number.
Save your work.
Repeat the Process for H2
Now you will repeat the procedure one more time to determine
the binary coefficient for carbon monoxide in Selexol. If you
need guidance, refer to the instructions in the step above.
Once you have completed this exercise. Save your work as
399tutor04.
Modifying the Binary Coefficients in the Full Model
Now that you have completed the tutorial model, open up the
Integrated Design UniSim model (your main model) and change
the binary coefficients so they match the numbers you obtained
from the tutorial process model(s).

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Change These Values

You have now completed the first tutorial exercise!

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Appendix

UniSim Customization

In Tools=>Preferences=>Resources=>Colours
Set PFD Background to white
Set PFD Label Text to black
Set PFD Annotation to black
In Tools=>Preferences=>Simulation
Uncheck Confirm Before Adding if Active Correlations
are Present
Uncheck Enable Cross Hairs on PFD

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