Design-001H Revised: Nov 7, 2012

Ammonia Synthesis with Aspen HYSYS® V8.0

Part 1 Open Loop Simulation of Ammonia Synthesis

1. Lesson Objectives
 Become comfortable and familiar with the Aspen HYSYS graphical user interface
 Explore Aspen HYSYS flowsheet handling techniques
 Understand the basic input required to run an Aspen HYSYS simulation
 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 HYSYS V8.0

3. Background
Ammonia is one of the most highly produced chemicals in the world and is mostly used in 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 which 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 from 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 HYSYS. 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 HYSYS
V8.0 user interface. A 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 Peng-Robinson equation of state
was chosen for this application.

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

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4. Aspen HYSYS Solution

Build a Process Simulation for Ammonia Synthesis

4.01. Start Aspen HYSYS V8.0. Select New on the Start Page to create a new simulation.

4.02. Create a component list. In the Component Lists folder, select Add. Add the following components to
the component list.

4.03. Create a fluid package. In the Fluid Packages folder, select Add. Select the Peng-Robinson property
package.

4.04. Define reactions. Go to the Reactions folder, and click Add. This will create a new reaction set called
Set-1. In Set-1, select Add Reaction and select Hysys, Conversion. This will create a new reaction called
Rxn-1.

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4.05. Double click on Rxn-1 to open the Rxn-1 window. Enter the following information. Close this window
when complete.

4.06. In Set-1, we must now attach the reaction set to a fluid package. Click the Add to FP button and select
Basis-1. The reaction set should now be ready.

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

4.08. From the Model Palette, add a Compressor to the main flowsheet.

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4.09. Double click the compressor (K-100) to open the property window. Create an Inlet stream called
SynGas, an Outlet stream called S2, and an Energy stream called Q-Comp1.

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4.10. We must define our SynGas feed stream. In K-100, go to the Worksheet tab. For the stream SynGas,
enter a Temperature of 280°C, a Pressure of 25.5 bar_g, and a Molar Flow of 7000 kgmole/h. In the
Composition form enter the following mole fractions. Stream SynGas should now solve.

4.11. Specify the compressor outlet pressure. In the Worksheet tab of K-100, enter a Pressure of 274 bar_g
for stream S2. The compressor should now solve.

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4.12. The flowsheet should look like the following.

4.13. Next, we will add a mixer. Add a Mixer to the flowsheet from the Model Palette.

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4.14. Double click on the mixer (MIX-100) to open the mixer window. Select stream S2 as the Inlet and create
an Outlet stream called S3. The mixer should solve. We will eventually use this mixer to connect a
recycle stream to the process.

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4.15. Next, add a heater to the flowsheet.

4.16. Double click on the heater (E-100) to open the heater window. Select S3 as the Inlet stream, create an
Outlet stream called S4, and create an Energy stream called Q-Heater. In the Parameters form in the
Design tab, enter a Delta P of 0. In the Worksheet tab, specify an outlet Temperature of 775 K
(481.9°C). Note that this heater is currently acting as a cooler, but once we connect the recycle stream
this block will in fact add heat and raise the temperature of the stream.

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4.17. Next, we will add a reactor to the flowsheet. This process uses plug flow reactors to accomplish
synthesis reaction, but for this simplified simulation we will use a conversion reactor. To use a plug flow
reactor, we would need to have detailed kinetics describing the reaction. Press F12 to open the UnitOps
window. Select the Reactors radio button and select Conversion Reactor. Click Add.

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4.18. After clicking Add, the conversion reactor window will open. Select an Inlet stream of S4 and create a
Vapour Outlet stream of S5V, a Liquid Outlet stream of S5L, and an Energy stream called Q-Reac.

4.19. In the conversion reactor window (CRV-100), go to the Reactions tab. Select Set-1 for Reaction Set. In
the Worksheet tab enter an outlet Temperature of 481.9°C for stream S5L. This value will copy over to
S5V. The reactor should then solve. Notice that the contents of the reactor are entirely vapor;
therefore the liquid outlet stream has a flowrate of zero.

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4.20. The flowsheet should now look like the following.

4.21. We will now add a cooler to cool the vapor stream leaving the reactor.

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4.22. Double click the cooler (E-101) to open the cooler window. Select stream S5V as the Inlet stream,
create an Outlet stream called S6, and create an Energy stream called Q-Cooler.

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4.23. In the Parameters form under the Design tab, enter a Delta P of 100 bar. We want to lower the
pressure in order to allow an easier separation of ammonia. In the Worksheet tab, specify an outlet
stream Temperature of 300 K (26.85°C). The cooler should solve.

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4.24. Add a separator block to the flowsheet.

4.25. Double click on the separator (V-100). Select an Inlet stream of S6, create a Vapour Outlet called S7,
and create a Liquid Outlet called NH3. The separator should solve.

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4.26. The flowsheet should now look like the following.

4.27. Review simulation results. Double click stream NH3. In the Conditions form under the Worksheet tab
you can view the stream flowrate and conditions. In the Composition form you can view the stream
composition. Here you can see that the mole fraction of ammonia is equal to 0.9754.

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4.28. After completing this simulation, you should save the file as a .hsc 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-
002H 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-002H Revised: Nov 7, 2012

Ammonia Synthesis with Aspen HYSYS® V8.0

Part 2 Closed Loop Simulation of Ammonia Synthesis

1. Lesson Objectives
 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 HYSYS
 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 HYSYS 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. Aspen HYSYS Solution:

In Part 1 of this series (Design-001H), 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 S7, shown below.

4.01. The first step will be to add a tee to separate the vapor stream S7 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.

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4.02. On the main flowsheet add a Tee block from the Model Palette. The tee block will fractionally split a
stream into several streams according to user specifications. Note that you can rotate the tee using the
Rotate button on the Flowsheet/Modify tab of the ribbon.

4.03. Double click the tee (TEE-100) to open the property window. Select S7 as the Inlet stream and create
two Outlet streams called Rec1 and Purge.

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4.04. In the Parameters form under the Design tab, enter a value of 0.01 for the Flow Ratio of the purge
stream. This means that 1% of the S7 stream will be diverged to the purge stream. The tee should solve.

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4.05. In order to recycle stream Rec1 back to the mixer, we must add a Recycle block to the flowsheet. The
recycle block is a theoretical block which acts to compare and modify the values of the outlet stream
until the inlet and outlet streams are equal to a specified tolerance.

4.06. Double click the recycle block (RCY-1). Select Rec1 as the Inlet stream and create an Outlet stream
called Rec2. The flowsheet should now look like the following.

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4.07. We need to add a compressor to raise the pressure of the recycle stream before we can connect it back
to the mixer. Add a Compressor to the flowsheet. Select Rec2 as the Inlet stream, create an Oulet
stream called Rec3, and create an Energy stream called Q-Comp2. Specify an outlet stream Pressure of
274 bar_g in the Worksheet tab. The compressor should solve and the flowsheet should look like the
following.

4.08. The recycle stream is now ready to be connected back to the mixer block to close the loop. Double click
on the mixer (MIX-100) to open the property window. Add stream Rec3 to the Inlet streams. The
flowsheet should solve.

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4.09. Check results. Double click on stream NH3. In the Composition form under the Worksheet tab you can
see that the mole fraction of ammonia is now 0.9581. This is below our desired mole fraction of 0.96.

Optimize the Purge Rate to Deliver Desired Product

4.10. We now wish determine the purge rate required to deliver a product with a mole fraction of 0.96
ammonia. Add an adjust block to the flowsheet.

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4.11. Double click the adjust block (ADJ-1) to open the adjust window. We must define our adjusted and
targeted variables. For the Adjusted Variable select Flow Ratio_2 of object TEE-100. To do this, click
the Select Var… button and select the following options. When finished select OK.

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4.12. Next, select the targeted variable. Choose Master Comp Mole Frac of Ammonia in stream NH3. This is
shown below. When finished click OK.

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4.13. Next, we will specify the target of 0.96 for the Mole Fraction of Ammonia in the product stream. The
adjust window should now look like the following.

4.14. Go to the Parameters tab and enter a Step Size of 0.001, and a Maximum Iterations of 1000. Click Start
to begin calculations. The adjust block should solve. Go to the Monitor tab to view results. You can see
that the mole fraction of ammonia in the product stream reached 0.96 at a purge fraction of 0.019.

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4.15. The flowsheet should now look like the following.

Investigate the Effect of Flash Feed Temperature on Product Composition

4.16. We would now like to determine how fluctuations in flash feed temperature will affect the product
composition. 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 of the product and recycle streams. First, we need to deactivate the adjust
block. Double click the adjust block and check Ignored.

4.17. In the navigation pane go to Case Studies and click Add.

4.18. A new case study called Case Study 1 will be created. In Case Study 1 click Add to add variables to the
study. First we will select the Mole Fraction of Ammonia in the product stream NH3.

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4.19. Next, we will add the Temperature of stream S6.

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4.20. We will vary the Temperature of stream S6 from 25°C to 100°C with a Step Size of 5°C.

4.21. Click the Run button, and then go to the Plots tab to view the results.

4.22. You will see that as temperature increases, the ammonia mole fraction decreases 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.

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5. 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-003H to being the economic
analysis.

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
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.

Welcome
https://drive.google.com/file/d/0BycPu1O9fk_GS055Tm93aHBwejA/view

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