Aspen HYSYS: Advanced Process Modeling Topics Reactors Workshop

Aspen HYSYS:
Advanced Process Modeling Topics
Reactors Workshop
Aspen HYSYS: Advanced Process Modeling Topics Reactors Workshop
Table of Contents
Reactors Workshop ........................................................................................................9 - 10
Reactors Solutions .........................................................................................................9 - 35
©2015 AspenTech. All Rights Reserved. 9-9 Aspen Technology, Inc.

Reactors Workshop
Files can be found in folder: 08_Reactors
Objective
This workshop will provide an overview of defining chemical reactions and reactor unit
operation models in Aspen HYSYS. You will also work with various logical operations
(Set, Spreadsheet, and Adjust models) to automate certain specifications and meet targets
in your model.
Description
In this module, you will simulate a Synthesis Gas Production facility. This will introduce
you to the reaction modelling capabilities of Aspen HYSYS.
The production of synthesis gas is an important step in the production of many different
chemical products. The main role of the synthesis gas plant is to convert natural gas,
primarily methane, into hydrogen. Synthesis gas is comprised of hydrogen, nitrogen,
carbon dioxide, and carbon monoxide. Typically the synthesis gas product is further
refined by removing carbon dioxide and carbon monoxide through amine contact,
pressure swing adsorption, or some other means. This workshop will focus on the
reaction portion of the process.
In most synthesis gas plants, four reactors are used. However in our simulation five
reactor unit operations will be used. This is because the combustion reaction, typically a
single vessel, will be modelled as two reactors in series with two different reaction types.
The first stage of the combustion will involve conversion-type reactions while the second
will involve equilibrium reactions.
This workshop includes the following tasks:
 Task 1 – Isolate the Natural Gas Feed

 Task 2 – Set up Reactions and Reaction Sets
 Task 3 – Build the Synthesis Gas Process
©2015 AspenTech. All Rights Reserved. 9 - 10 Aspen Technology, Inc.

Task 1 – Isolate the Natural Gas Feed

One of the products from your turbo expander/NGL fractionation plant is a high pressure
gas product, mainly consisting of methane. It has been decided to split off a fraction of
this gas product for sale to a neighboring plant with a synthesis gas production facility.
In your HYSYS simulation, you need to isolate the desired amount of natural gas flow for
transmission to the Syn Gas Plant. The natural gas also needs to be brought to the proper
conditions for the Syn Gas process. Set up these items in the first part of the workshop.
 Start the exercise with your HYSYS simulation utilized in the last workshop (07-
ColumnPSV.hsc).
 If the HYSYS file is still in the Safety Analysis Environment, click on the
Simulation button to return to the Simulation Environment.
 Viewing the main flowsheet, locate the portion with the K-101 compressor, material
stream 15, the Export Gas compressor, and the Sales Gas stream.
 Break the connection between stream 15 and Export Gas Comp.

 Add a Tee to the flowsheet and define it as follows:
In This Cell... Enter...
Connections
Name Gas Split
Inlet 15
Outlets Export Gas

To Syn Gas
Worksheet
To Syn Gas, Molar Flow 90 kgmole/h (198.4 lbmole/hr)
 Connect the Export Gas stream to the inlet of the Export Gas Comp.
The Synthesis Gas Process will be modeled within your current workshop flowsheet. But
to avoid having a main flowsheet window with excessive amounts of operations and
streams, you’ll make use of the sub-flowsheet modeling capability of Aspen HYSYS and
place the Syn Gas Process inside its own sub-flowsheet. This should help to better
organize your growing process model!
 From the Object Palette, add a Blank Sub-Flowsheet and select the option to Start
With a Blank Flowsheet.
 Double-click the sub-flowsheet icon that now appears on your main flowsheet. On
the Connections tab rename the sub-flowsheet as Syn Gas Plant.
 List To Syn Gas as an External Stream in the Inlet Connections list.
 Click the Sub-Flowsheet Environment… button to view the Syn Gas Plant sub-
flowsheet.
The To Syn Gas material stream you see in the sub-flowsheet is a mixture of light and
medium hydrocarbons, CO2, nitrogen, and a small amount of water. This stream needs
to be compressed and heated to certain conditions before it can enter the synthesis gas
reactor train.

It’s also important to consider the components present in the stream and how/if they’ll
react in the synthesis gas process. To Syn Gas is primarily composed of methane, but
there are also small amounts of ethane, propane, butanes, etc. As part of the synthesis
gas process, combustion of methane is a reaction of interest. But of course if methane
is present and combusted, it can be reasoned that any other hydrocarbons would be
combusted as well. To simplify the reaction definitions, you’ll remove any
hydrocarbons heavier than propane prior to feeding the gas into the first reactor, thus
ignoring the combustion of any heavier hydrocarbons.
 Add a Compressor to the Syn Gas Plant sub-flowsheet. Set it up with the
following connections and conditions:

Connections
Name Natural Gas Comp
Inlet To Syn Gas
Outlet HP Gas
Energy QK-NGC
Worksheet
HP Gas, Pressure 3500 kPa (507.6 psia)
 The HP Gas stream needs to feed into the reaction section at 90 °C. Use a Heater
model to do this.
Connections
Name Natural Gas Heater
Inlet HP Gas
Outlet Hot HP Gas
Energy Q-NGH
Parameters
Delta P 0 kPa (0 psi)
Worksheet
Hot HP Gas, Temperature 370 °C (698 °F)
 The last step before setting up the reactions and reactors is to remove all
hydrocarbons heavier than propane from the reactor train feed. Use the HYSYS
Component Splitter unit operation to do this. It can be added from the Columns
section of the Object Palette:

 After adding the Component Splitter, define it as follows:

Connections
Name Remove Heavy HC
Inlet Hot HP Gas
Overhead Outlet Natural Gas
Bottoms Outlet Heavy HC
Energy Q-Split
Parameters
Stream Specifications Use Stream Flash Specifications
Equalize All Stream Pressures
Natural Gas Temperature 370 °C (698 °F)
Heavy HC Temperature 370 °C (698 °F)
 Move to the Design | Splits form. For Natural Gas, enter a split of 1.0 for
Nitrogen, CO2, Methane, Ethane, Propane, and H2O.
 Enter a split of 0.0 for all other species.

 Save your case as 08-Reactors.hsc.
Task 2 – Set up Reactions and Reaction Sets

The definition of any chemical reactions to be considered within a HYSYS flowsheet
must be made in the Properties Environment. All tools and features needed for
specifying various classes of reactions are available there. Once the reactions have been
define, specified, and properly assigned to the active Fluid Package they can be used in
the Simulation Environment. One more thing to consider – make sure any components
needed for the reactions are specified in your component list!
 Return to the Properties Environment. Note that there are two Component Lists
and two Fluid Packages present.

 The Basis-1 Fluid Package and Component List-1 are the active items for the Syn
Gas Plant sub-flowsheet, so select Component List-1 from the Navigation Pane.
 Add the following components to the list: CO, Hydrogen, and Oxygen.
 Staying in the Properties Environment, select the Reactions folder on the
Navigation Pane and click the Add button to create a new Reaction Set.
 Alternatively you can click on the Reactions icon on the Home tab of the ribbon.
 Click back on the Reactions folder in the Navigation Pane. Under the Name field,
re-name the created Reaction Set (Set-1) as Combustor Rxn Set.
 Select the Combustor Rxn Set folder in the Navigation Pane; then click the Add
Reaction button at the bottom of the Reaction Set window.
 Make sure the Reactant Source is set as HYSYS and choose Conversion as the
reaction type. Then click Add Reaction.

 Click Add Reaction four more times. You should have five reactions total (Rxn-1,
Rxn-2, Rxn-3, Rxn-4, and Rxn-5) when finished. Then you may close the Add
Reactions window.
 Expand the Combustor Rxn Set folder in the Navigation Pane; you should see the
five reactions listed. Click on Rxn-1 to view it.
 In the Stoichiometry Info section, list out Methane, H2O, CO, and Hydrogen.
List their stoichiometric coefficients as -1.0, -1.0, 1.0, and 3.0 respectively.
In the Basis section, make sure Methane is shown as the Base Component and
enter a percentage conversion of 35% in the Co field.
 Check your inputs for Rxn-1 against the figure below:

 Continue by defining the other four Conversion reactions in the Combustor Rxn
Set. Use the following characteristics:
Name Reaction Base Component Co
Rxn-2 CH4 + 2H2O  CO2 + 4H2 Methane 65
Rxn-3 CH4 + 2O2  CO2 + 2H2O Methane 100
Rxn-4 2C2H6 + 7O2  4CO2 + 6H2O Ethane 100
Rxn-5 C3H8 + 5O2  3CO2 + 4H2O Propane 100
 After defining the reaction stoichiometry data and conversions, return to the
Combustor Reaction Set folder and click on the Add to FP button.

 Select the Basis-1 Fluid Package, and then click Add Set to Fluid Package.
 Click back on the Reactions folder in the Navigation Pane and click Add to add a
new Reaction Set.
 Rename this Reaction Set as Shift Rxn Set.
 Click the Add Reaction button in the Shift Rxn Set and choose Equilibrium as the
reaction type.
 View the created reaction (Rxn-6) and click the Library tab.

 Highlight the reaction with the form: CO + H2O   CO2 + H2. Click Add
Library Rxn to set this as the reaction for Rxn-6.
 Go back to the Shift Rxn Set folder and click on the Add to FP button. Add this
reaction set to the Basis-1 Fluid Package.
 Return to the Reactions folder in the Navigation Pane and add one more Reaction
Set; title it Reformer Rxn Set.
 View the Reformer Rxn Set menu and click the pull-down arrow on the Add
Reaction button. Select the Existing Reaction option.

 Add Rxn-1 and Rxn-2 to the Reformer Rxn Set.

 Click on the Add to FP button to attach this set to the Basis-1 Fluid Package.
 All necessary reactions and reaction sets have been added. Save your case.

Task 3 – Build the Synthesis Gas Process

There are six different reactor unit operation types in Aspen HYSYS. By using
combinations of these six operations, virtually any real reactor can be modeled given
sufficient information. The six reactor types available are Conversion, Yield Shift,
Equilibrium, Gibbs, Continuously Stirred Tank Reactor (CSTR), and a Plug Flow
Reactor (PFR).
The Conversion Reactor calculates the composition of the outlet stream given the
stoichiometry of all the reactions occurring and the conversion of the base component.
The Yield reactor does the same given an implied yield for each component.
In the case of the Equilibrium Reactor, it determines the composition of the outlet stream
given the stoichiometry of all reactions occurring and the value of the equilibrium
constant (or the temperature dependent parameters that govern the equilibrium constant)
for each reaction. The Gibbs Reactor valuates the equilibrium composition of the outlet
stream by minimizing the total Gibbs free energy of the effluent mixture.
In the case of the CSTR, it assumes that the reactor contents are completely mixed in
computing the outlet stream conditions, given the stoichiometry for all the reactions that
are occurring and the kinetic rate constant (or the temperature dependence parameters for
determining the kinetic constant) for each reaction. The PFR assumes that the reaction
stream passes through the reactor in plug flow in computing the outlet stream
composition, given the stoichiometry of all the reactions occurring and a kinetic rate
constant for each reaction.
For the synthesis gas reactions, you’ll be making use of the Conversion and Equilibrium
reactor models. Follow the steps below to build these reactors and their associated
operations.
 Click on the Simulation Environment button.

 If your flowsheet appears to be un-solved, return to the Parent Flowsheet (click Go
to Parent) in the Flowsheet/Modify ribbon tab) and allow the main flowsheet to
solve.
Hint: You may see a message about a “Fatal Error.” Check your Demethanizer column
to ensure that it solved. If it did not, open the column property view and click the Reset
button, and then Run it. If you receive a Consistency Error message, just click to make
the Solver Active. The main flowsheet should solve at this point. If you have any further
problems check with your instructor.
 Locate the Syn Gas Plant sub-flowsheet icon. Double-click on it and re-enter the
sub-flowsheet.
 Create three new Material Streams with the following inputs:

Name Reformer Air Combustor

Steam Steam
Temp., °C (°F) 250 (482) 16 (60.8) 250 (482)
Pressure, kPa (psia) <empty> <empty> <empty>
Molar Flow, kgmole/hr 240 (529.1) 90 (198.4) 140 (308.6)

(lbmole/hr)
Molar Composition 100% - H2O 79% - N2 100% - H2O

21% - O2
The first reactor in the synthesis gas plant is the Reformer. This reactor will be modelled
as a Conversion Reactor and it will utilize the Reformer Reaction Set.
 From the Object Palette, go to the Columns section and select the Conversion
Reactor to add it into the flowsheet.
 Name this reactor Reformer and attach Natural Gas and Reformer Steam as
inlets.
 Name the Vapour Outlet Combustor Feed and the Energy stream as Reformer-Q.
 Even though there will be no liquid flow from this reactor, we still must create a
liquid phase product stream for flowsheet connectivity purposes. Name the liquid
product stream as Reformer LP.

 Move to the Reactions | Details page and select Reformer Rxn Set as the Reaction
Set. This will automatically connect the proper reactions to this reactor.

 Once the reaction set is attached, select the Conversion% radio button.
 Select Rxn-1 from the Reaction drop down menu and change the Co value to be
40%.
 Do the same for Rxn-2 and choose Co to be 30%.
Note: You have the ability to alter reaction specifications from their original settings
after you install them in a reactor block. This capability provides helpful flexibility to
adjust reaction data without having to go back into the Properties Environment.
 On the Worksheet tab, enter a temperature of 930 ºC (1706 ºF) for the outlet
stream Combustor Feed.
At this stage, the first reactor will not solve yet. The pressure is unknown in the
Reformer Steam stream. As you build the flowsheet, you’ll use a logical operation (Set)
to define this pressure. But you’ll add the next reactor in the sequence first.
The second reactor in a synthesis gas plant is the Combustor. The Combustor will be
modelled as a Conversion reactor and an Equilibrium reactor in series. This is because
Conversion reactions and Equilibrium reactions cannot occur in reactors of the opposite
type. That is, conversion reactions cannot be associated with equilibrium reactors, and
vice versa.
 Add another Conversion Reactor with the following data:


Connections
Name Combustor
Inlets Air, Combustor Steam,
Combustor Feed
Vapour Outlet Mid Combust
Liquid Outlet Combustor LP
Reactions | Details
Reaction Set Combustor Rxn Set
Rxn-1 Conversion 35% (Default)
Recall that we did not enter any pressure data for the Air or Steam streams. To provide
the necessary pressures, we will use a pair of logical operations to call in known pressure
data on another material stream. First we’ll use the Set operation to link stream
pressures, and then we’ll apply the Spreadsheet operation as an alternate approach.
 Select the Set Operation from the Common section of the Object Palette.
 Select Reformer Steam | Pressure as the Target Variable. Define Natural Gas
as the Source Object.

 On the Parameters tab and ensure the Multiplier is set at 1 and the Offset at 0.
For this pressure association, we want equality between the two stream pressures, so
a multiplier of 1 and an offset of 0 will result in this type of relationship.
You also need to set the pressures of Air and Combustor Steam. Rather than take the Set
operation approach and require two additional unit operations, you can use a Spreadsheet.
You’ll find that a single Spreadsheet can do the same calculations as two Set operations.
 Add a Spreadsheet from the Object Palette. Rename it as Pressure Assignment.

 Move to the Spreadsheet tab and provide the following labels:

A1 Natural Gas Pressure
A3 Air Pressure
A4 Combustor Steam Pressure
 Right-click in cell B1 and select the Import Variable option. Select Natural Gas |
Pressure from the variable browser menu.
 Enter the following formulas into the cells indicated:

B3 =B1*1
B4 =B1*1
 Right-click on cell B3 and select the Export Formula Result option. Select Air |
Pressure from the variable browser menu.
 Do the same for cell B4, exporting this result to the Combustor Steam material
stream.
 What is the calculated heat flow/duty of the Reformer?
As mentioned before, the Combustor is to be modelled as a Conversion reactor followed

by an Equilibrium reactor, so you must still add the Equilibrium side of the combustion.
The Shift Reactors will also be modelled as Equilibrium Reactors. Therefore, a total of
three equilibrium reactors must be added to complete the flowsheet.
 Add an Equilibrium Reactor from the Columns section of the Object Palette with
the following information:


Connections
Name Combustor Shift
Inlet Mid Combust
Vapour Outlet Shift1 Feed
Liquid Outlet Combustor Shift LP
Reactions | Details
Reaction Set Shift Rxn Set
S
 What is the calculated outlet temperature from the combustion section of the
reaction train?
 Add another Equilibrium Reactor with the following information:

Connections
Name Shift1
Inlet Shift1 Feed
Vapour Outlet Shift2 Feed
Liquid Outlet Shift1 LP
Energy Stream Shift1-Q
Reactions | Details
Worksheet
Shift2 Feed, Temperature 450 °C (842 °F)
 How much energy must be removed from Shift1 to meet the desired outlet
temperature?
 Add the third and final Equilibrium Reactor with the following information:


Connections
Name Shift2
Inlet Shift2 Feed
Vapour Outlet Synthesis Gas
Liquid Outlet Shift2 LP
Energy Stream Shift2-Q
Reactions | Details
Worksheet
Synthesis Gas, Temperature 400°C (752°F)
 What is the molar flow rate of hydrogen in the Synthesis Gas stream?
 What is the molar flow rate of nitrogen in the Synthesis Gas stream?
 What is the ratio of hydrogen to nitrogen in the Synthesis Gas stream? What is the
easiest way to calculate this value in HYSYS? (E.g. not using a calculator, MS
Excel, etc.)
 Save your case.

To control the temperature of the product stream leaving the combustion section (the
Shift1 Feed stream), the flow rate of steam to the Combustor Conversion reactor
operation is manipulated. It is desired to have an outlet temperature from the combustion
section of 930°C (1706°F). The steam flow can be adjusted manually until the desired
temperature is achieved. However, this might take a lot of time and will not be
automatically updated if something else in the process were to change. You can utilize
the Aspen HYSYS Adjust operation to adjust/manipulate one variable until the desired
condition is met for a define target variable.
 Select the Adjust unit operation from the Object Palette and add it to the flowsheet.
 Attach the Adjusted Variable, Target Variable, and Target Value as shown:
 On the Parameters tab, enter the Step Size as 20 kgmole/h (44 lbmole/hr) and
define a Minimum of 0 kgmole/h.

A second Adjust operation will be used to manipulate the Air stream flow rate. This is
important as the Air flow rate determines the ratio of hydrogen to nitrogen in the
synthesis gas product. We want this value to be set at 3.5.
Since a component ratio is not a normally available HYSYS variable, it needs to be
calculated within the program and made available to other features. This is a great
opportunity to apply the HYSYS Spreadsheet. So if you did not already create a
Spreadsheet to compute the hydrogen-to-nitrogen ratio in the Synthesis Gas stream, you
might want to do so now!

 Add another Adjust operation to your flowsheet. Select Air | Molar Flow as the
Adjusted Variable.
 For the Target Variable, select the Spreadsheet operation containing your
calculated hydrogen-nitrogen ratio as the Object, and the cell containing that value
as the Variable.
 Set a Specified Target Value of 3.5.
 On the Parameters tab, ensure a Tolerance of 0.001 is specified and define a Step
Size of 20 kgmole/hr (44 lbmole/hr).
In certain HYSYS simulations, solving two Adjust operations might result in the two
interfering with one another while they solve. This is because changing either one of the
adjusted variable may affect both target variables simultaneously. To prevent this
interference, the Adjusts can be set to solve simultaneously by using a different solution
algorithm.
 On the Parameters tab of the ADJ-1 operation, select the Simultaneous Solution
checkbox.

 Repeat this procedure for the second Adjust operation, ADJ-1.

 Start the simultaneous Adjusts solving by clicking the Start button on either Adjust
block.
 You can also open the Adjust Manager menu from the Home tab in the ribbon.
The Adjust Manager allows you to manage and solve any and all simultaneously
solved Adjust blocks through a common interface.
 Start the Adjust calculations and allow them to solve. You may need to initiate the
calculations from one Adjust rather than the Adjust Manager to get things started.
 What is the new Air stream molar flow rate?
 What is the molar flow rate of the Synthesis Gas product?

 Save your case.

Challenge Exercise
The Gibbs Reactor can be used to represent both equilibrium and constrained equilibrium
systems. Replace the Shift2 Equilibrium Reactor with a Gibbs Reactor, and specify the
same outlet temperature
 Make the appropriate changes to the Gibbs Reactor to ensure the results are
consistent with the original simulation.
 Save your case as 08-ReactorsChallenge.hsc.
Recommended Reading
Knowledge Base Solution 111551
How does HYSYS calculate the energy balance around a reactor?
Knowledge Base Solution 113034:

Can I prioritize the reactions in a Conversion Reactor?
Knowledge Base Solution 126847

Equilibrium reactor predicts carbon formation while the Gibbs Reactor does not. Why?

Aspen HYSYS: Advanced Process Modeling Topics Reactors Workshop

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Advanced Process Modeling Topics

©2015 AspenTech. All Rights Reserved. 9-9 Aspen Technology, Inc.

This workshop includes the following tasks:

 Task 1 – Isolate the Natural Gas Feed

©2015 AspenTech. All Rights Reserved. 9 - 10 Aspen Technology, Inc.

Task 1 – Isolate the Natural Gas Feed

 Break the connection between stream 15 and Export Gas Comp.

©2015 AspenTech. All Rights Reserved. 9 - 11 Aspen Technology, Inc.

 Add a Tee to the flowsheet and define it as follows:

In This Cell... Enter...

Name Gas Split

Outlets Export Gas

To Syn Gas, Molar Flow 90 kgmole/h (198.4 lbmole/hr)

©2015 AspenTech. All Rights Reserved. 9 - 12 Aspen Technology, Inc.

In This Cell... Enter...

In This Cell... Enter...

Name Natural Gas Heater

Outlet Hot HP Gas

Delta P 0 kPa (0 psi)

Hot HP Gas, Temperature 370 °C (698 °F)

©2015 AspenTech. All Rights Reserved. 9 - 13 Aspen Technology, Inc.

 After adding the Component Splitter, define it as follows:

In This Cell... Enter...

©2015 AspenTech. All Rights Reserved. 9 - 14 Aspen Technology, Inc.

 Save your case as 08-Reactors.hsc.

Task 2 – Set up Reactions and Reaction Sets

©2015 AspenTech. All Rights Reserved. 9 - 15 Aspen Technology, Inc.

©2015 AspenTech. All Rights Reserved. 9 - 16 Aspen Technology, Inc.

©2015 AspenTech. All Rights Reserved. 9 - 17 Aspen Technology, Inc.

Name Reaction Base Component Co

Rxn-2 CH4 + 2H2O  CO2 + 4H2 Methane 65

Rxn-3 CH4 + 2O2  CO2 + 2H2O Methane 100

Rxn-4 2C2H6 + 7O2  4CO2 + 6H2O Ethane 100

Rxn-5 C3H8 + 5O2  3CO2 + 4H2O Propane 100

©2015 AspenTech. All Rights Reserved. 9 - 18 Aspen Technology, Inc.

©2015 AspenTech. All Rights Reserved. 9 - 19 Aspen Technology, Inc.

©2015 AspenTech. All Rights Reserved. 9 - 20 Aspen Technology, Inc.

 Add Rxn-1 and Rxn-2 to the Reformer Rxn Set.

©2015 AspenTech. All Rights Reserved. 9 - 21 Aspen Technology, Inc.

Task 3 – Build the Synthesis Gas Process

 Click on the Simulation Environment button.

©2015 AspenTech. All Rights Reserved. 9 - 22 Aspen Technology, Inc.

Name Reformer Air Combustor

Temp., °C (°F) 250 (482) 16 (60.8) 250 (482)

Pressure, kPa (psia) <empty> <empty> <empty>

Molar Flow, kgmole/hr 240 (529.1) 90 (198.4) 140 (308.6)

Molar Composition 100% - H2O 79% - N2 100% - H2O

©2015 AspenTech. All Rights Reserved. 9 - 23 Aspen Technology, Inc.

©2015 AspenTech. All Rights Reserved. 9 - 24 Aspen Technology, Inc.

 Add another Conversion Reactor with the following data:

©2015 AspenTech. All Rights Reserved. 9 - 25 Aspen Technology, Inc.

In This Cell... Enter...

©2015 AspenTech. All Rights Reserved. 9 - 26 Aspen Technology, Inc.

 Add a Spreadsheet from the Object Palette. Rename it as Pressure Assignment.

In This Cell... Enter...

In This Cell... Enter...

As mentioned before, the Combustor is to be modelled as a Conversion reactor followed

©2015 AspenTech. All Rights Reserved. 9 - 27 Aspen Technology, Inc.

In This Cell... Enter...

 Add another Equilibrium Reactor with the following information:

In This Cell... Enter...

©2015 AspenTech. All Rights Reserved. 9 - 28 Aspen Technology, Inc.