Department of Chemical Engineering

Elective CE433: Molecular Modelling of Fluids

Modelling the phase equilibria of a carbon

dioxide + methane + ethane mixture with the
PR EOS using Aspen properties

Use the Peng-Robinson equation of state in Aspen-properties to study the phase behaviour of a
three-component mixture containing carbon dioxide, methane and ethane at fixed temperature
T=220K and pressure P=20 bar. We will first investigate in some detail each of the binary
mixtures in order to confirm that the equation of state chosen and the Aspen calculations are
adequate, will correlate binary parameters for one of the mixtures, and finally obtain the phase
diagram of the three-component mixture.

1. Deliverables (hand-in by 09:00 Wednesday 3 December):

1. Pxy plot for CO2+ethane at T=210K and T=230K comparing the experimental data and
the calculated data.
2. Pxy plot for methane+ethane at T=210K and T=230K comparing the experimental data
and the calculated data.
3. Pxy plot for CO2+methane at T=220K and T=240K comparing the experimental data and
the two sets of calculated data. One set of calculated data is obtained using the kij
binary parameter given by Aspen and the other set of calculated data is obtained with
your own correlated value of kij. Provide the two values of kij used.
4. Triangle phase diagram of the CO2+methane+ethane mixture at fixed T=220K and fixed
P=20 bar comparing the experimental data and the calculated data.
5. Confirm that the ternary phase diagram is correct by studying the binary information
previously obtained. Write a short summary (half a page maximim) of your conclusions.
In detail, you should complete the following tasks:
CO2+methane
1. Input all the experimental data provided in Excel and plot in Pxy form identifying the
liquid and gas phases.
2. Run a calculation in Aspen at the same fixed temperatures.
3. Plot the results of the Aspen calculation with the Peng-Robinson equation together with
the experimental data (usually experimental data is represented with symbols and
calculations with lines)
4. Perform a regression of the kij binary parameter at T=240K.
5. Use the new value of kij to run calculations at T=220K and T=240K again and compare
the new results with the experimental data and previous calculations.
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Elective CE433: Molecular Modelling of Fluids

CO2+ethane
Follow points 1-3 above.
Methane+ethane
Follow points 1-3 above.
CO2+methane+ethane
1. Input all the experimental data provided in Excel and plot in Pxy form identifying the
liquid and gas phases.
2. Perform a calculation in Aspen with the Peng-Robinson equation using your correlated
kij parameter for the CO2+methane mixture.
3. Plot the results of the Aspen calculation with the Peng-Robinson equation together with
the experimental data in a triangle plot.

2. Using Aspen:
Launch Aspen v8.4 using Application Jukebox
Create new simulation: File New Blank Simulation Create
The simulation opens automatically in Properties Components Specifications
1. Enter Component Ids:
1.
2.
3.
4.
5.

Click Find
Enter component name and click Find Now
Highlight desired component in list proposed by Aspen
Click Add Selected Components
Repeat 2-4 until all components are entered, then click Close

Click on Next (the blue N in the Home menu). Aspen automatically moves to the next input
form. Fill in the following input forms:
2. Preparing an input:
1. Methods Specifications Global tab: Select Peng-Robinson property model under
Base method
2. Setup Specifications Global tab: Enter a title of your choice and select SI units
3. Write down in your notes all the parameters that appear in Methods Parameters
Binary Interaction PRKBV-1.
4. Click Next N to go to next and select Run Property Analysis/Setup to load
calculations with the parameters currently selected in the Parameters Table.
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Department of Chemical Engineering

Elective CE433: Molecular Modelling of Fluids

3. To run a binary phase equilibrium calculation

1. In the Analysis section of the Home menu, select Binary. This opens a new case which
appears in Properties Analysis.
2. In the Binary Analysis tab, under Analysis type select Txy. Specify the Valid phases,
Pressure, and Composition sections (calculate 50 data points).
3. Click on Run Analysis. A plot of the results is generated automatically. (To regenerate
the plot at a later time, go to the Results subsection of the analysis case and in the Plot
section of the Home menu select the Txy plot.)
4. To add experimental data
Inputting experimental data sets, for example Txy data:
1. Go to Properties Data, and click New
2. Name the data set and select data type MIXTURE.
3. In the Setup tab select the Components in the mixture, the Data type (TXY), the
Pressure, and the Composition Basis (Mole fraction).
4. In the Data tab enter the experimental data in the Excel file provided.
5. On the Plot section of the Home menu, click on T-xy to generate a plot of the data.
6. Repeat steps 1-5 for all data sets.
To plot the Txy experimental data alongside the Txy analysis calculations:
1. Plot the analysis results and the data set (see above), and keep both tabs open.
2. Go to the analysis results plot.
3. In the Design menu click on Merge Plot and select the data set plot from the drop-down
list. (If any other plots are open, the list will also include these.) The analysis results plot
will be updated to include the experimental data.
5. To perform a correlation of binary parameters
1. Select Regression from the Run Mode section of the Home menu.
2. Click on New and name the regression case.
3. In the Setup tab select the Method (PENG-ROB) and the Data set for regression by
clicking on the drop-down list.
4. In the Parameters tab set up the parameters to be regressed. For the CO2-Methane kij:
Type: Binary parameter
Name: PRKBV
Element: 1
Component or group: CO2, Methane
Usage: Regress
Set Aij=Aji: Yes.
5. Click on Next N and select Run Data Regression cases.
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Department of Chemical Engineering

Elective CE433: Molecular Modelling of Fluids

6. When the regression is complete, you can change the existing kij with the regressed one
by clicking yes on the pop-up window which appears. Otherwise it can be changed
manually by going to Methods Parameters Binary Interaction PRKBV-1.
To see the result of the correlation, go to the Results subsection of the regression case. Note
that the parameter describing the CO2-methane interactions is different from the original one
provided by Aspen. Write the value in your notes. Select the new parameter in the parameter
table (see step 6 above) and follow Part 3 above to perform a new analysis calculation with the
new parameter.
6. To calculate phase equilibria in multicomponent systems
In the case of calculations with more than two components, Aspen requires information of
which properties should be calculated (the Property Set). We shall perform constant pressure
and constant temperature flash calculations. The outputs are the compositions of the three
components in the liquid and vapour phases.
First ensure all the input corresponding to the relevant three components and chosen kij is
complete.
Go to Properties Property Sets, select New and provide a name.
In the Properties tab select mole fraction under Physical properties.
In Qualifiers tab create two columns and select vapour and liquid phases.
To carry out a flash calculation follow: Run Mode Analysis New and provide a
name.
5. Select type GENERIC.
6. In the System tab:
- Select Points along a flash curve.
- Specify the Valid phases as Vapour-Liquid
- Select an initial composition of flow for each component (be careful that your total
composition is inside the expected coexistence region)
7. In the Variables tab:
- Specify the pressure and temperature conditions
- In the Adjusted variables section, specify mole fraction of CO2.
- Click on Rage/List and select Specify Limits: calculate for mole fractions from 0 to 1
using 20 points.
1.
2.
3.
4.

8. In the Tabulate tab select your Property Set.

9. Click on Next N and select Run Property Analysis to carry out the calculation.
10. Go to the Results subsection of the analysis case and transfer the data to Excel for
plotting.

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Elective CE433: Molecular Modelling of Fluids

Department of Chemical Engineering

7. To build-up a triangle phase diagram in Excel.

In a triangular phase diagram each of the axes corresponds to the mole fraction of one of the
components. The experimental and calculated compositions need to be scaled in order for the
points to follow triangular geometry. Each of the points along the coexisting vapour and liquid
phase can be transformed to be given by (X,Y) which can then be plotted directly. Follow:
X = 1 xmethane - xco2/2
Y = xco2*cos(/6)
Following this transformation the vortices of the phase diagram are:

CO2

Methane

Ethane

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