EP313

Chemical Process Simulation and Design

L4 – Reactor
Tab Description
Components Allows access to a component list which is associated with a fluid package.
When adding a new component list or editing a current list, the Component
List View opens. This view is designed to simplify adding components to the
case.
Fluid Pkgs Allows you to create and manipulate all fluid packages for the simulation
case. Also, you can assign a fluid package to each flowsheet that exists
within the case and select a Default fluid package, which is automatically
used for all new flowsheets.
Hypotheticals Allows individual Hypotheticals and Hypothetical Groups to be defined for
installation into any fluid package.
Oil Manager Allows access to the Oil Environment where you can input assay data,
cut/blend an oil and define pseudo components for installation in any
existing fluid package.
Reactions Allows you to install reaction components, create reactions, create reaction
sets, attach reactions to reaction sets and attach reaction sets to any
existing
fluid package.
Component Allows you to specify composition across fluid package (sub-flowsheet)
Maps boundaries.
User Property Create and make user properties available to any fluid package.
3. Reaction
Library reactions within UniSim Design are defined inside
the Reaction Manager and the components are
automatically transferred to the fluid package.
Reaction Type Requirements
Conversion Requires the stoichiometry of all the components in the
reaction and the conversion of a base component in the
reaction.
Equilibrium Requires the stoichiometry of all the reactions. The reaction
order for each component is determined from the
stoichiometric coefficients.
Heterogeneous Requires the stoichiometry of all the components in the
Catalytic reaction and the parameters of the reaction kinetics including
the surface reaction kinetic parameters in the numerator term
and the adsorption kinetic parameters in the denominator
term.
Kinetic Requires the stoichiometry of all the components in the
reaction, as well as the Activation Energy and Frequency Factor
in the Arrhenius equation for reactions. The forward and
reverse orders of reaction for each component can be
specified.
Simple Rate Requires the stoichiometry of all the components in the
reaction, as well as the Activation Energy and Frequency Factor
in the Arrhenius equation for the forward reaction.
Reaction Type Requirements
Conversion stoichiometry and conversion.
𝑋% = 𝐶0 + 𝐶1 𝑇 + 𝐶2 𝑇 2

Equilibrium stoichiometry and equilibrium coefficients.

𝐾𝑒𝑞 = 𝑓 𝑇

Heterogeneous stoichiometry and reaction kinetics & adsorption kinetic. i.e

Catalytic 𝑎 𝑏 𝐶𝑅𝑟 𝐶𝑆𝑠
𝑘 𝐶𝐴 𝐶𝐵 −
𝐾
−𝑟𝐴 = 𝛾
1 + 𝐾𝑖 𝐶𝑖 𝑖

Kinetic stoichiometry and Arrhenius equation (forward & backward).

𝜑 𝛾
𝑟𝐴 = −𝑘𝑓 𝐶𝐴𝑎 𝐶𝐵𝑏 + 𝑘𝑟𝑒𝑣 𝐶𝑅 𝐶𝑆

Simple Rate stoichiometry and Arrhenius equation (forward). i.e.

Langmuir-Hinshelwood
𝜑 𝛾
𝑎 𝑏 𝐶𝑅 𝐶𝑆
𝑟𝐴 = −𝑘𝑓 𝐶𝐴 𝐶𝐵 −
𝑘𝑒𝑞
Available Unit Operations in UNISIM
CSTR

freely licensed media file

Yuri r at the Yuri Raysper project
http://www.processengr.com/
http://www.processengr.com/
 Copyright Armfield Limited, Ringwood, UK

Copyright W2 Energy, Inc., Carson City, NV

PFR

http://www.indiamart.com/
http://www.cnoocshell.com/
Reactor & Type of reaction match-up
Name Reaction Types

Conversion Reactor Conversion

Equilibrium Reactor Equilibrium Coefficient

Gibbs Reactor With/Without stoichiometry

Simple rate, Heterogeneous Catalytic,

CSTR Reactor
Kinetic.
Simple rate, Heterogeneous Catalytic,
PFR Reactor
Kinetic.
Conversion Reactor
1. Reaction does not require any
thermodynamic knowledge.
2. ONLY input stoichiometry concept &
conversion of basis reactant.
3. The reaction will proceed until
• Specified conversion has been reached OR
• A limiting reagent has been exhausted.

Objective: To simulate the reactor based on the

conversion of basis reactant.
Definition of conversion
• In defining conversion, we choose one of the
reactants as the basis of calculations

FA,in FA,out

𝐹𝐴,𝑜𝑢𝑡 = (1 − 𝑋𝐴 )𝐹𝐴,𝑖𝑛
Exercise 1: Create Simulation basis

The reforming reaction of natural gas

(methane) with steam to produce hydrogen
and carbon monoxide:
𝐶𝐻4 + 𝐻2 𝑂 → 3𝐻2 + 𝐶𝑂
Objective: Setup the conversion reactor w 75%
conversion of CH4:
1. Components  𝐶𝐻4 , 𝐻2 𝑂 , 𝐻2 , 𝐶𝑂
2. Fluid Package  Peng-Robinson/PSRV/etc.
3. Reactions
Create Simulation basis

1. Components

2. Fluid Package
Property Package: Peng-Robinson
Create Simulation basis (Cont.)
3. Reactions

B C
A

D
Create Simulation basis (Cont.)
3. Reactions (Complete)

B C
A

D
Check Components and Properties package

A
Create Simulation basis (Cont.)
3. Reactions

A
Create Simulation basis (Cont.)
3. Reactions 𝐶𝐻4 + 𝐻2 𝑂 ↔ 3𝐻2 + 𝐶𝑂
Create Simulation basis (Cont.)
3. Reactions 𝐶𝐻4 + 𝐻2 𝑂 ↔ 3𝐻2 + 𝐶𝑂
Create Simulation basis (Cont.)
3. Reactions

C
B

A
Create Simulation basis (Cont.)
Create Simulation basis (Cont.)

B C

D
Create Simulation basis (Cont.)
3. Reactions (Complete)
• What we have learned?
Setup the reaction based on stoichiometric
and conversion values.

Food-of-Thought: What if we have

multiple reactions in one reactor? i.e.
𝐴 + 𝐵 ↔ 3𝐶 + 𝐷
𝐴 + 2𝐵 ↔ 𝐶 + 𝐸

How to setup this reactions chain?

Exercise 2: Simulation of Conversion Reactor

Once a simulation basis is completed, we can

proceed to simulation environment.
Simulation of Conversion Reactor
Design & nfo
Simulation of Conversion Reactor
Reactions
Q1 - The reactor is an isothermal process,
What is the product stream composition?

Is there any different

between 100c.f and 10c.f of
reactor VOLUME? S-S: NO
D-S: YES
Q2 – Repeat Q1, What is the product stream
composition if 100% conversion of CH4?
When to attach/or not to attach
energy stream?
• If you need to specify the temperature outlet, you need
to attach energy stream to the reactor.
• The energy stream will calculate the heat of reaction,
Qrxn required by the reactor. This will tell you whether
the reactor is releasing or consuming heat. Very
important for determining heating or cooling
requirement for the reactor
• However, if you know your reactor will be adiabatic (i.e.
Qrxn = 0, no heat exchange with surrounding), then you
don’t need to attach energy stream. In this case, the
outlet temperature will be calculated based on energy
balance
Model a conversion reactor
exercise
• Model the following reaction process as conversion
reaction
• Ethylbenzene dehydrogenation to styrene
• Conversion: 65%
• C6H5CH2CH3 ---> C6H5CH=CH2 + H2
• Inlet reactor condition:
• Temperature: 650 C
• Pressure: 1 bar
• Ethylbenzene flow: 10000 kgmol/hr
Model a conversion reactor
exercise
• Simulate the adiabatic reactor condition
• What is the temperature of the product outlet?
• Simulate the reactor as isothermal reactor
• How much heat consumed/released by the reactor?
• For both cases above, what is component molar
flowrate of the product outlet?
• See if you can get the same numbers by manual
calculations (still remember material balance
calculations for reactive system?)
Modeling multiple reactions
system
• Refer to the hand-out of Conversion Reaction part
• After you have done the handout, do the
conversion reactor exercise
Equilibrium Reactor
• The Equilibrium reactor is a unit operation block
that models equilibrium reactions.
• The outlet streams of the reactor are in a state of
chemical and physical equilibrium.

Objective: To examine the product composition at

the reactor outlet using a given equilibrium constant
and operating condition
 Equilibrium reactions (theory)

or in pressure form

Use a given formula for Kc or Kp to calculate product composition at the reactor outlet.
Kc and Kp is usually is a function of temperature.
Exercise 3: Water gas shift reaction
The reaction has been employed for 40 years in the
industrial process for H2 production from liquid and
gaseous hydrocarbons. The role of the WGS reaction
is to increase the H2 yield and decrease the CO
concentration (lower than 10-20 ppm), which is a
poison for some catalysts used.
𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐻2 + 𝐶𝑂2
The reaction equilibrium is given by (Smith et al., 2010) as
5693.5
ln 𝐾𝑒𝑞 = + 1.077 ln 𝑇 + 5.44 × 10−4 𝑇 − 1.125 × 10−7 𝑇 2 − 13.148
𝑇

Q: Determine the actual conversion of CO

 B

A
Reactions
𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐻2 + 𝐶𝑂2
Set the basis parameters
 Reactions
5693.5
ln 𝐾𝑒𝑞 = + 1.077 ln 𝑇 + 5.44 × 10−4 𝑇 − 1.125 × 10−7 𝑇 2 − 13.148
𝑇
Q: Determine the actual conversion of CO by simulating equilibrium reactor

Q: Is the reactor adiabatic or

non-adiabatic?

Q: What is the molar fraction

of H2 in the reactor product?
Determine the conversion of WGS reaction if condition of the reactor change

To investigate the effect of molar flowrate of H2O stream to the reactor

performance as defined by percent conversion of reaction and H2 compo in
the product stream.
How to plot graph in UniSim
Step 1: Complete the simulation (NO error!!!)
Step 2: Identify the parameters for y-axis and x-axis.
y-axis: %conversion & Mole Frac of H2 (dependent)
x-axis: Molar flow (H2O) (independent)
Step 3: Tools  Databook OR Ctrl+D
Step 4: Variables Tab  Insert the parameters
Step 5: Case Studies Tab  Add  select dep & ind
Step 6: Click View  Set Low & High and Step size
Step 7: Click Start button
End: Click Result button and graph will pop-up
 Q: Determine the actual conversion of CO if the reactor is operated with specified
temperature

Q: What is the heat of reaction? Is it

exothermic or endothermic reaction?
Exercise 4: Modeling water gas shift
reaction via GibbS reactor
The reaction has been employed for 40 years in the
industrial process for H2 production from liquid and
gaseous hydrocarbons. The role of the WGS reaction
is to increase the H2 yield and decrease the CO
concentration (lower than 10-20 ppm), which is a
poison for some catalysts used.
𝐶𝑂 + 𝐻2 𝑂 ↔ 𝐻2 + 𝐶𝑂2
Steps: Define components, select fluid package, enter
simulation environment without defining the reaction