Thermo-014 Revised: October 29, 2012

Retrograde Behavior Illustrated with Aspen Plus® V8.0

1. Lesson Objectives
 Observe retrograde behavior

2. Prerequisites
 Aspen Plus V8.0

3. Background
For a mixture, the amount of liquid (liquid fraction) increases as pressure increases at constant temperature.
However, in the retrograde region near the critical region, we may see some interesting behavior - vapor
fraction increases as pressure increases (at constant temperature).

Many mixtures have retrograde behavior near the critical region. In this example, we will examine the
retrograde behavior using a binary mixture of ethane and pentane.

The examples presented are solely intended to illustrate specific concepts and principles. They may not
reflect an industrial application or real situation.

4. Problem Statement and Aspen Plus Solution

Problem Statement

Retrograde behavior can be observed in the mixture of ethane and pentane. In Aspen Plus, use PT Envelope to
determine the critical region of the mixture. Then, use Sensitivity Analysis to examine the retrograde behavior
near the critical region.

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Aspen Plus Solution

If you are unfamiliar with how to start Aspen Plus, select components, define methods, or construct a flowsheet,
consult Get Started Guide for New Users of Aspen Plus.pdf for instructions.

4.01. Create a new simulation in Aspen Plus using the Blank Simulation template. The Components |
Specification | Selection sheet is displayed. Enter ETHANE and PENTANE for Component ID. Enter
C5H12-1 in the Alias column for Pentane.

4.02. Go to the Methods | Specifications sheet. Select PENG-ROB as the Base method for this module.

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4.03. Press F4 key. Note that the Methods | Parameters | Binary Interaction | PRKBV-1 | Input sheet is
displayed and binary parameters are filled automatically.

4.04. Before entering the Simulation environment, we would like to look at the PT envelope to determine the
retrograde region near the critical region. Create a new PT envelope analysis by selecting the PT-
Envelope button in the Analysis group in Home tab of the ribbon.

4.05. Go to the Analysis | PTENV-1 | Input | System sheet, select Mass from the first drop-down list on the
sheet. Enter 50 in Flow column for both ETHANE and PENTANE as shown below.

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4.06. Click Run analysis button to generate the PT envelope. The retrograde behavior can be observed around
120°C and between 55 and 67 bar. The graph legend can be moved by clicking and dragging to better
view the upper right hand region of the envelope.

4.07. Enter the Simulation environment. Move to the Simulation environment by clicking the Simulation bar
in the navigation pane. Add a Heater and its inlet and outlet streams in the main flowsheet. The Heater
can be found under the Heat Exchangers tab under Model Palette. Rename the streams to INLET and
OUTLET. Rename the heater block to HX-101 as shown below.

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4.08. Go to the Streams | INLET | Input | Mixed sheet (or double click the INLET stream) to specify
information of the INLET stream. Enter 115 for Temperature and 55 for Pressure. In the Composition
frame, select Mass-Flow. Then, enter 50 for both ETHANE and PENTANE in Value column as shown
below.

4.09. Go to the Blocks | HX-101 | Input | Specifications sheet (or double click the heater unit on the main
flowsheet) to specify the information for the heater. Enter 115 for Temperature and 58.38 for Pressure.

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4.10. Go to the Blocks | HX-101 | Input | Flash Options sheet, and enter 100 for Maximum iterations and 1e-
06 for Error tolerance.

4.11. Click the Run | Run button under the Home tab of the ribbon (or press F5) to run the simulation.
Simulation should complete without any error or warning.

4.12. In the navigation pane, click Model Analysis Tools | Sensitivity. The object manager for Sensitivity is
displayed. Click New… button to create Sensitivity block called S-1.

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4.13. Go to the Model Analysis Tools | Sensitivity | S-1 | Input | Vary sheet. Create a new variable by
clicking Variable no drop-down list and then clicking <New> in the drop-down list.

4.14. Then, select Block-Var for Type, HX-101 for Block, and PRES for Variable. In Values for varied variable
frame, select Overall range radio button. Enter 58.78 for Lower, 68.78 for Upper and 0.04 for Incr.

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4.15. Go to the Model Analysis Tools | Sensitivity | S-1 | Input | Define sheet. Click New… button to create
a new variable named PRES. Select Blocks for Category, Block-Var for Type, HX-101 for Block, and PRES
for Variable.

4.16. Repeat the previous step to create another variable called TEMP. Select Blocks for Category, Block-Var
for Type, HX-101 for Block, and TEMP for Variable.

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4.17. We create yet another variable called VFRAC in a similar manner. Select Streams for Category, Stream-
Var for Type, OUTLET for Stream, MIXED for Substream, and VFRAC for Variable.

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4.18. Go to the Model Analysis Tools | Sensitivity | S-1 | Input | Tabulate sheet and click the Fill variables
button. Then, click the Run | Run button under the Home tab of the ribbon (or press F5) to run the
simulation.

4.19. The results of varying pressure in heater block are generated and can be seen by navigating to Model
Analysis Tools | Sensitivity | S-1 | Results | Summary sheet. Note that VFRAC increases as PRES
increases, which is called a retrograde behavior. Note that you need to scroll down to Row/Case 187 to
see the results as shown below.

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4.20. A plot can be generated for the results obtained from Sensitivity analysis by clicking the Plot | Results
Curve button under the Home tab of the ribbon. The Results Curve window pops up.

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4.21. Select VFRAC to be the variable used in the plot and select OK. The plot of VFRAC versus PRES is
generated as shown below.

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5. Conclusions
For the binary mixture of ethane and pentane (50% each on mass basis), we observed that vapor fraction
increases from 0.701457 to 1 as pressure increases from 65.22 bar to 66.78 bar, which is a retrograde behavior.
This retrograde behavior can be a source of multiple solutions to process simulation.

6. Copyright
Copyright © 2012 by Aspen Technology, Inc. (“AspenTech”). All rights reserved. This work may not be
reproduced or distributed in any form or by any means without the prior written consent of
AspenTech. ASPENTECH MAKES NO WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH
RESPECT TO THIS WORK and assumes no liability for any errors or omissions. In no event will AspenTech be
liable to you for damages, including any loss of profits, lost savings, or other incidental or consequential
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this work. This work and its contents are provided for educational purposes only.

AspenTech®, aspenONE®, and the Aspen leaf logo, are trademarks of Aspen Technology, Inc.. Brands and
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