Design-001 Revised: Oct 18, 2012

Ammonia Synthesis with Aspen Plus® V8.0

Part 1 Open Loop Simulation of Ammonia Synthesis

1. Lesson Objectives
 Become comfortable and familiar with the Aspen Plus graphical user interface
 Explore Aspen Plus flowsheet handling techniques
 Understand the basic input required to run an Aspen Plus simulation
 Understand the various classes of reactor models available
 Learn how to approximate the ‘real’ kinetic-based, heterogeneous reaction into an equilibrium
reaction
 Determine the appropriate reactor model type
 Determination of Physical Properties method for Ammonia Synthesis
 Apply acquired skill to build an open loop Ammonia Synthesis process simulation
 Enter the minimum input required for an simplified Ammonia Synthesis model
 Examine the open loop simulation results

2. Prerequisites
 Aspen Plus V8.0

3. Background
Ammonia is one of the most highly produced chemicals in the world and is mostly used as fertilizers. In 1913
Fritz Haber and Carl Bosch developed a process for the manufacture of ammonia on an industrial scale (Haber-
Bosch process). This process is known for extremely high pressures that are required to maintain a reasonable
equilibrium constant. Today, this process produces 500 million tons of nitrogen fertilizer per year and is
responsible for sustaining one-third of the Earth’s population.

Ammonia is produced by reacting nitrogen from air with hydrogen. Hydrogen is usually obtained fro m steam
reformation of methane, and nitrogen is obtained from deoxygenated air. The chemical reaction is shown
below:

Our goal is to produce a simulation for the production of ammonia using Aspen Plus. We will create a very
simplified version of this process in order to learn the basics of how to create a flowsheet in the Aspen Plus
V7.3.2 user interface. A process flow diagram for this process is shown below.

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Knowledge Base: Physical Properties for Ammonia Process

Equation-of-state models provide an accurate description of the thermodynamic properties of the high-
temperature, high-pressure conditions encountered in ammonia plants. The Redlich-Kwong modification RKS-
BM was chosen for this application.

Find more information of Redlich-Kwong-Soave-Boston-Mathias (RKS-BM) method from Aspen Plus on-
line help:

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Knowledge Base: Reactor Model Types

Aspen Plus includes three types of reactor models. The type you choose depends on the level of rigor
you want to use and the amount of information you have available:

Reactors
in Aspen Plus

Balance Equilibrium Kinetic

Based Based Based
RYIELD, RSTOIC REQUIL, RGIBBS RCSTR, RPLUG, RBATCH

(1) Balance Based (RYIELD, RSTOIC) - These reactors are for mass and energy balance purposes. You specify
the conversion or yield and the reaction stoichiometry. In essence, you tell Aspen the expected result
and it handles the details of the mass, energy, and species balances.

(2) Equilibrium Based (REQUIL, RGIBBS) - These reactor models are appropriate for fast reactions that reach
equilibrium quickly (although there are ways to specify approach to equilibrium for non-ideal cases).
RGIBBS is the most flexible model. It allows multiple phases (including multiple solid phases) and
multiple species. This model uses Gibbs free energy minimization to predict results. It requires accurate
thermodynamics since Gibbs energy is calculated from enthalpy and entropy.

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(3) Kinetic-Based, aka. Rate-Based (RCSTR, RPLUG, RBATCH) - These reactor models are appropriate when
you know the reaction kinetics. You describe kinetics using one of the built-in reaction models (power
law, LHHW, etc.) or your own user-defined kinetic subroutine. RBATCH and RCSTR are able to represent
reactors with solid-phase catalysts. RPLUG can represent tubular or multi-tube plug flow reactors. RCSTR
represents any well mixed stirred tank (or fluid bed) reactors. RBATCH is for batch reactors. These
reactor models are more predictive, but they require more information to describe reaction rates.

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

4. Aspen Plus Solution

Build a Process Simulation for Ammonia Synthesis

4.01. Start Aspen Plus V8.0. Select New on the Start Page, select Blank and Recent | Blank Simulation, press
the Create button. We choose blank for this process because templates have default property methods,
unit sets, and databanks selected. When using a specific method, such as RKS-BM, it is best to choose
blank to ensure that the correct property method is selected.

4.02. In Properties view, go to Components | Specifications, select components: H2, N2, CH4, AR, CO, and
NH3.

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4.03. Go to Methods | Specifications. In the drop-down Method name combo box, find RKS-BM and select it.
After that, click on Methods | Parameters | Binary Interaction | RKSBV-1, it will retrieve the binary
interaction parameters to complete RKS-BM for use in the simulation. If these parameters do not
populate, make sure that the databank EOS-LIT is selected in the Databanks tab under RKSBV-1.

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Design-001 Revised: Oct 18, 2012

4.04. Go to the simulation environment. For that, click on the Simulation button in the bottom left of the
screen. Then find the Main Flowsheet tab. The Main Flowsheet is the main simulation flowsheet where
you will create a simulation.

4.05. In the Simulation view, you can find Main Flowsheet as well as Model Palette (F10) where you can find
all the Aspen Plus models and streams.

Main Flowsheet

Model Palette

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(FAQ) Useful Option To Know: Automatically Assign Block/Stream Name with Prefix

Description: Have blocks/streams automatically assigned a name beginning with the specified character string.
For example, if B is entered for block’s prefix, the blocks will be named B1, B2, B3, etc. By default, B is used for
block’s prefix and S is used for stream’s prefix. When this option is off, Aspen Plus will prompt you to enter an ID
each time a block or a stream is created. To enable and disable this option, go to File menu, find the Option
button (as shown below), you could find two checkboxes to set these options on and off.

4.06. Find the following models from the Model Palette, and drop them onto the flowsheet.

Compressor Mixer Heater RStoic Heater Flash2

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4.07. Find Material Stream from the Model Palette, and use it to connect model blocks.

4.08. Select all blocks and streams; and find Align (Ctrl + B) to align all blocks automatically. You can also right
click a stream and select Align, or select a section of the flowsheet and right click to select Align. You
could try Reroute Stream (Ctrl + J) to reroute streams. These tools will help you to manage flowsheets
and keep them organized and easy to read.

4.09. Make your simulation flowsheet as neat as possible. It is a very good habit that will really help you in the
future when you need to deal with very complex simulations, which can include hundreds of model
blocks on a single flowsheet.

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4.10. Also it is good to provide a meaningful name for each model block. For instance, use C-xxx for
compressor, M-xxx for mixer, E-xxx for heat exchanger or heater, etc. Press Ctrl + M to rename a block.
Also rename feed and product streams as shown below.

(FAQ) How to Change Unit of Measure

Description: A units set is a collection of unit specifications for each dimensional quantity used in Aspen Plus.
Aspen Plus provides these basic units sets: International system units (SI), English engineering units (ENG), and
Metric engineering units (MET). You can change the global unit set in the ribbon. Use the units selector on the
Home tab to select a unit set:

Tip: In the Home tab ribbon, find Unit Sets

button to create your own unit sets.

This unit set specification applies to all forms. When you change these units, Aspen Plus changes the units on all
forms to the ones from the specified units set, and converts the values.

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4.11. Specify feed stream (SYNGAS). Double click on the stream labeled SYNGAS on the main flowsheet or
navigate to Streams | SYNGAS | Input.
• T = 553.15 K, P = 26.17 atm
• Component Mole-Flow: H2 = 5160 kmol/hr, N2 = 1732 kmol/hr, CH4 = 72 kmol/hr, AR = 19 kmol/hr,
CO = 17 kmol/hr

4.12. Configure/Specify Compressor (C-100). Double click the compressor block (C-100) or navigate to Blocks
| C-100 | Setup.
• Isentropic Compressor
• Discharge pressure = 271.4 atm

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4.13. Configure/Specify Mixer (M-100). Double click on the mixer block (M-100) or navigate to Blocks | M-
100 | Input.
• Verify that the input sheet contains a 0 in the Pressure spec. Note that in the Pressure field, if you
enter a number greater than 0, this will be the discharge or operating pressure. If you enter a
number less than or equal to zero, this will be the pressure drop through the unit.

4.14. Configure/Specify Heater (E-100). Double click on the heater block (E-100) or navigate to Blocks | E-100
| Input.
• Temperature = 755 K (Outlet temperature)
• Heater with zero pressure drop – enter 0 in the Pressure spec

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4.15. Configure/Specify Reactor (R-100). Double click the reactor (R-100) or navigate to Blocks | R-100 |
Setup.
• Reaction temperature and pressure: 755 K, 270 atm

4.16. Go to the Reactions tab and click New to specify the reaction.

• Reaction Stoichiometric Coefficients: N2=-1, H2 = -3, NH3 = +2

N2 + 3H2 = 2NH3
• Specify Product Regeneration: Fractional conversion = 40% of the reactant N2

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4.17. Configure/Specify Heater (E-101). Double click on the heater (E-101) or navigate to Blocks | E-101 |
Input.
• Actually, this is a ‘cooler’, cooling to 300.15 K
• No pressure drop – enter 0 for the Pressure spec

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4.18. Configure/Specify Flash Drum (FLSH-100). Double click the flash drum (FLSH-100) or navigate to Blocks
| FLSH-100 | Input.
• No additional heat; Heat Duty = 0
• No pressure drop – enter 0 for the Pressure spec

4.19. Check if the simulation is all set to run:

• Your simulation should be all set to run. To check if you have missed any data to enter, press Next
Input (F4) button in the Home ribbon:

4.20. Click OK to run the simulation. Open Control Panel (F7) to check if the simulation calculations
completed with or without any errors or warning.

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4.21. Review simulation results:

• Display Stream Results on Flowsheet

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(FAQ) Flowsheet Display Option – Enabling More Stream Results Visible on Flowsheet

Description: In the Modify ribbon, you can access the ‘Flowsheet Display Option’ which allows you to change the
following results to visible or invisible.

• Temperature, Pressure, Vapor Fraction

• Heat/Work
• Mole flow rate, Mass flow rate, Volume flow rate

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4.22. Use Stream Summary to display all stream results in a single view: In the Home tab, find Stream
Summary button in Summary group.

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4.23. After completing this simulation, you should save the file as a .bkp file. It is also good practice to save
periodically as you create a simulation so you do not risk losing any work. The open loop simulation is
now ready to add a recycle stream, which we will then call a closed loop simulation. See module Design-
002 for the closed loop design.

5. 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
damages arising out of the use of the information contained in, or the digital files supplied with or for use with,
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
product names mentioned in this documentation are trademarks or service marks of their respective companies.

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Design-002 Revised: Oct 18, 2012

Ammonia Synthesis with Aspen Plus® V8.0

Part 2 Closed Loop Simulation of Ammonia Synthesis

1. Lesson Objectives
 Review Aspen Plus convergence methods
 Build upon the open loop Ammonia Synthesis process simulation
 Insert a purge stream
 Learn how to close recycle loops
 Explore closed loop convergence methods
 Optimize process operating conditions to maximize product composition and flowrate
 Learn how to utilize the model analysis tools built into Aspen Plus
 Find the optimal purge fraction to meet desired product specifications
 Determine the effect on product composition of a decrease in cooling efficiency of the pre -flash
cooling unit

2. Prerequisites
 Aspen Plus V8.0
 Design-001 Module (Part 1 of this series)

3. Background; Recap of Ammonia Process

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

4. Review of Aspen Plus Convergence Methods

There are several methods Aspen Plus can utilize to converge recycle loops. Convergence in Aspen Plus is an
iterative process consisting of making guesses for tear streams and then comparing the calculated stream values
with the guessed values. If these values are equivalent within a certain tolerance, then the simulation h as
successfully converged. Consider the following example shown in the flowsheet below:

To calculate the properties of stream S4, the properties of stream S2 must be known or calculated. To calculate
the properties of stream S2, the properties of streams S1 and S4 must be known or calculated. In mathematical
terms we have:

( )

( )

The mutual dependency of streams S4 and S2 creates an algebraic loop. This loop can be removed by ‘tearing’ a
stream apart. For example, we can choose to hypothetically tear stream S4 into two separate streams. This
would result in the following flowsheet:

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Mathematically we now have the following:

( )
( )

There is no longer mutual dependency between streams S4 and S2. The issue now relies in finding a solution
that results in stream S5 being equal to stream S4. This is accomplished by utilizing iterative convergence
methods which are briefly described below. Based on the flowsheet you create, Aspen Plus will automatically
define tear streams to converge, or alternatively you can input user defined tear streams.

The following methods are available in Aspen Plus:

 Direct substitution
 Wegstein
 Newton
 Secant
 Broyden
 Sequential quadratic programming (SQP)

The direct substitution method is a slow but sure way to reach convergence. For each iteration, this method
uses the values calculated from the previous flowsheet pass as the new values of the tear stream. In
mathematical terms we have the following, where k is the iteration number.

( )

This sequence would be iterated until and are equivalent within a specified tolerance.

The Wegstein method is an extrapolation of the direct substitution method used to accelerate converge nce. It
attempts to estimate what the final solution will be based on the difference between successive iteration values.
This is the default convergence method for system generated tear convergence blocks and is usually the
quickest and most reliable method for tear stream convergence.

Newton’s convergence method for simultaneous nonlinear equations uses matrices of partial derivatives to
obtain a set of linear equations which are then solved. This process is iterated until convergence criteria are met.
Newton’s method requires the evaluation of the function and it’s derivative per iteration. This method provides
an efficient means of convergence only if a sufficiently good initial guess is provided. Use the Newton method
for tear streams only when the number of components is small or when convergence cannot be achieved by
other methods.

The secant method uses a succession of roots of secant lines to approximate the root of a function. Compared
with Newton’s method, the secant method does not require the evaluation of the functions derivative. This
enables this method to converge for systems involving non-elementary functions. The secant method can be

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Design-002 Revised: Oct 18, 2012

used for converging single design specifications and is the default method in Aspen Plus for design specification
convergence.

Broyden’s method is a modification of the Newton and secant methods that uses approximate linearization
which can be extended to higher dimensions. This method is faster than Newton’s method but is often not as
reliable. Broyden’s method should be used to converge multiple tear streams or design specifications, and is
particularly useful when converging tear streams and design specifications simultaneously.

Sequential quadratic programming is an iterative method for flowsheet optimization. This method is useful for
simultaneous convergence of optimization problems with constraints and tear streams.

5. Aspen Plus Solution

In Part 1 of this series (Design-001), the following flowsheet was developed for an open loop Ammonia Synthesis
process.

This process produces two outlet streams; a liquid stream containing the ammonia product and a vapor stream
containing mostly unreacted hydrogen and nitrogen. It is desired to capture and recycle these unreacted
materials to minimize costs and maximize product yield.

Add Recycle Loop to Ammonia Synthesis Process

Beginning with the open loop flowsheet constructed in Part 1 of this series, a recycle loop will be constructed to
recover unreacted hydrogen and nitrogen contained in the vapor stream named OFFGAS , shown below.

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Design-002 Revised: Oct 18, 2012

5.01. The first step will be to add a Splitter to separate the OFFGAS stream into two streams; a purge stream
and a recycle stream. As a rule of thumb, whenever a recycle stream exists, there must be an associated
purge stream to create an exit route for impurities or byproducts contained in the process. Often times
if an exit route does not exist, impurities will build up in the process and the simulation will fail to
converge due to a mass balance error.

5.02. On the main flowsheet add an FSplit block located in the Mixers/Splitters tab in the Model Palette. The
FSplit block will fractionally split a stream into several streams according to user specifications. Rename
this block S-100 and connect the OFFGAS stream to the inlet port. Construct two material outlet streams
and label one as the purge stream. This is shown below. Double click on the splitter block to specify the
split fraction. Enter a value of 0.01 for the Split fraction of the purge stream. This means that 1% of the
OFFGAS stream will be diverged to the purge stream.

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5.03. Next, we must add a compressor to bring the pressure of the recycle stream back up to the feed
conditions. Add a compressor (Compr) block from the Pressure Changers tab in the Model Palette.
Connect stream S7 to the inlet port and construct a material stream for the outlet port. Remember that
you can rotate and resize the block icons by right clicking the block and selecting either Rotate Icon or
Resize Icon.

5.04. Double click on the compressor block to specify the operating conditions. Select Isentropic as the Type
and enter a Discharge pressure of 271 atmospheres.

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5.05. The recycle stream is now ready to be connected back to the mixer block to close the loop. Right click on
the recycle stream, select Reconnect Destination, and connect the stream to the inlet port of the mixer
block. This can also be done by double clicking the arrow of the disconnected recycle stream. This
stream (S8) will be the tear stream in this simulation. Aspen Plus automatically recognizes and assigns
tear streams; however you can also specify which streams you would like to be tear streams.

5.06. Open the Control Panel and run the simulation (F5). You should result in an error stating that block C-
101 is not in mass balance and that the simulation failed to converge after 30 iterations.

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There are several steps you can take to overcome this issue. First, check to see which convergence
method is being used and check which stream is being converged. Scroll up to the very top of the
Control Panel.

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5.07. Aspen Plus is using the Wegstein method to converge recycle stream S8. The Wegstein method is a
good method to use when trying to converge a single recycle stream, and stream S8 is an appropriate
stream to attempt to converge. The next thing you can do is to check the maximum error per iteration
to see whether the solver is heading towards convergence or not. In the navigation pane, go to
Convergence | Convergence | $OLVER01 | Results. In the Summary tab you can see which variables
have converged and which haven’t after 30 iterations. Click the Tear History tab where you can view
the maximum error that occurs each iteration and which variable it occurs in. Click the Custom plot
button at the top of the screen.

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5.08. Select Iteration as the x-axis and Maximum error/Tolerance as the y-axis. Change the y-axis min to -
5000 and change the max to 5000. The plot should appear as below.

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5.09. By looking at the plot, it is clear that the Wegstein method is on the right track towards fin ding the
solution. It may be that the solver just needs a few more iterations to converge. In the navigation pane,
go to Convergence | Options | Methods. Click the Wegstein tab and increase the Maximum flowsheet
evaluations to 50. Run the simulation again. In the control panel you will see that the solver has now
converged after only 20 iterations. This is because the solver used the last calculation from the previous
run that failed to converge as the initial guess for the second run. If you reinitialize and run the
simulation again you will notice that the simulation converged after 49 iterations.

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5.10. Now that the simulation has converged, check the results. In the Home ribbon click Stream Summary
and then click Stream Table.

This will generate a stream table that will appear on the main flowsheet. Here you can see the flow and
composition of each stream.

Optimize the Purge Rate to Deliver Desired Product

5.11. We now wish determine the purge rate required to deliver a product with a mole fraction of 0.96
ammonia. First, check the composition of the current ammonia stream by clicking on the product stream
(LIQ-NH3) and clicking Stream Analysis | Composition in the Home ribbon. Select Mole for Composition
basis and press Go.

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From the composition analysis results, the mole fraction of ammonia in the product stream is only
0.955, which is below the specification of 0.96. We need to determine the purge rate required to reach
this product specification.

5.12. Go to the navigation pane and select Flowsheeting Options | Design Spec and click New. This will
create a design spec which we will use to vary the purge fraction in order to reach 0.96 mole fraction
ammonia in the product stream.

5.13. Under the Define tab select New. Enter the variable name NH3FRAC. A window will appear where you
must define the variable. Select Mole-Frac as type, LIQ-NH3 for Stream, and NH3 for Component.

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5.14. Next, move to the Spec tab and enter NH3FRAC for Spec, 0.96 as Target, and 0.0001 for Tolerance.

5.15. Move to the Vary tab and define the purge fraction from the splitter as the manipulated variable. Select
Block-Var for Type, S-100 for Block, FLOW/FRAC for Variable, and Purge for ID1. Enter 0.01 and 1 as the
Upper and Lower limits and a Step size of 0.001.

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5.16. Open the Control Panel and run the simulation (F5). Go to Flowsheeting Options | Design Spec | DS-1 |
Results. You will see that the mole fraction of ammonia in the product stream has reached 0.96 at a
purge fraction of 2.48%.

Investigate the Effect of Flash Feed Temperature on Product Composition

5.17. We would now like to determine how fluctuations in flash feed temperature will affect the product
composition and flowrate. Changes in cooling efficiency or utility fluid temperature can change the
temperature of the flash feed stream. This change in temperature will change the vapor fraction of the
stream, thus changing the composition and flowrate of the product and recycle streams. To do this
analysis go to Model Analysis Tools | Sensitivity and click New. Define the Manipulated variable to be
the Outlet temperature of the cooler block (E-101). Enter a Temperature range from 300 to 350 K for a
total of 10 points.

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5.18. In the Define tab, define the variables that you wish to measure, in this case ammonia mole fraction
and flowrate in the product stream.

5.19. In the Tabulate tab, select which variables you wish to view results for. Manually enter the variables
that you just created, or press the Fill variables button.

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5.20. Before running the simulation, be sure to deactivate the design spec we created in Flowsheeting
Options. This can be done by going to Flowsheeting Options and right clicking on the design spec and
selecting Deactivate. Once this is done, run the simulation. Check results by going to Model Analysis
Tools | Sensitivity | S-1 | Results. Click the Results Curve plot button on the Home ribbon. Select both
Mole fraction and Flowrate to plot against the varied parameter on the x-axis.

The results plot should look like the following.

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5.21. You will see that as temperature increases, both the product flowrate and product quality decrease,
which means that when operating this process it will be very important to monitor the flash feed
temperature in order to deliver high quality product.

6. Conclusion
This simulation has proved the feasibility of this design by solving the mass and energy balances. It is now ready
to begin to analyze this process for its economic feasibility. See module Design-003 to being the economic
analysis.

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7. 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
damages arising out of the use of the information contained in, or the digital files supplied with or for use with,
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
product names mentioned in this documentation are trademarks or service marks of their respective companies.

19