INTRODUCTION TO

Chemical Reaction
Engineering Module
Introduction to the Chemical Reaction Engineering
Module
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Part number: CM021602

Contents

Introducing the Chemical Reaction Engineering Module . . . . . . 5

Chemical Reaction Engineering Simulations . . . . . . . . . . . . . . . . . 6
Modeling Strategy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Investigating Chemical Reaction Kinetics — Modeling Perfectly
Mixed and Plug Flow Reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Investigating Reactors and Systems — Modeling Space Dependency9
Chemical Reaction Engineering Module Interfaces . . . . . . . . . . 11
The Physics Interface List by Space Dimension and Study Type . 15
Tutorial Example: NO Reduction in a Monolithic Reactor. . . . 18
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Tutorial Modeling Strategy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Chemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Single Channel Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Investigating a 3D Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Note on the Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Modeling Instructions: Single Channel Model . . . . . . . . . . . . . . . 36
Modeling Instructions: 3D Reactor Model . . . . . . . . . . . . . . . . . 52

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4|
Introducing the Chemical Reaction Engineering Module

The Chemical Reaction Engineering Module is tailor-made for the modeling of

chemical systems primarily affected by chemical composition, reaction kinetics,
fluid flow, and temperature as functions of space and time. It has several interfaces
to model chemical reaction kinetics: mass transport in dilute, concentrated and
electric potential-affected solutions, laminar and porous media flows, and energy
transport.
Included in these interfaces are the kinetic expressions for reacting systems, in bulk
solutions and on catalytic surfaces, and models for the definition of mass transport.
You also have access to a variety of ready-made expressions in order to calculate a
system’s thermodynamic and transport properties.
While a major focus of the module is on chemical reactors and reacting systems, it
is also extensively used for systems where mass transport is the major process. This
includes unit operations equipment, separation and mixing processes,
chromatography, and electrophoresis. The module is also widely used in
educational and training courses to explain chemical engineering, chemical
reaction engineering, electrochemical engineering, biotechnology, and transport
phenomena.
In addition to its application in traditional chemical industries, it is a popular tool
for investigating clean technology processes (for example, catalytic monoliths and
reactive filters) for applications such as microlaboratories in biotechnology and in
the development of sensors and equipment in analytical chemistry.

An overview of the interfaces and their functionality can be found in Chemical

Reaction Engineering Module Interfaces.

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Chemical Reaction Engineering Simulations

Simulations in chemical reaction engineering are often used during the

investigation and development of a reaction process or system.
In the initial stages, they are used to dissect and understand the process or system.
By setting up a model and studying the results from the simulations, engineers and
scientists achieve the understanding and intuition required for further innovation.
Once a process is well understood, modeling and simulations are used to optimize
and control the process’ variables and parameters. These “virtual” experiments are
run to adapt the process to different operating conditions.
Another use for modeling is to simulate scenarios that may be difficult to
investigate experimentally. One example of this is to improve safety, such as when
an uncontrolled release of chemicals occurs during an accident. Simulations are
used to develop protocols and procedures to prevent or contain the impact from
these hypothetical accidents.
In all these cases, modeling and simulations provide value for money by reducing
the need for a large number of experiments or to build prototypes, while,
potentially, granting alternative and better insights into a process or design.

6|
Modeling Strategy
The flowchart in Figure 1 describes a strategy for modeling and simulating
chemical reaction processes and systems.

Figure 1: Flowchart summarizing the strategy for modeling reacting systems or designing chemical
reactors.

The strategy suggests first investigating a reacting system that is either

space-independent, or where the space dependency is very well-defined.
A system where space dependency is irrelevant is usually so well mixed that
chemical species concentrations and temperature are uniform throughout and are

|7
only a function of time — this is often denoted as a perfectly mixed reactor. A plug
flow reactor is a system where the space dependency is well defined.
Once the effects of space dependency are removed or well accounted for, both
experimental and modeling investigations can concentrate on the reactions
themselves, and the rate laws that control them.
The next step is to apply this information to the chemical reactors or systems that
are of interest. These, of course, vary in length, width and height, and are also
subject to a range of external parameters including inflows, outflows, cooling, and
heating. These are space (and time) dependent systems.

Investigating Chemical Reaction Kinetics — Modeling Perfectly Mixed

and Plug Flow Reactors
An important component in chemical
reaction engineering is the definition of the
respective reaction rate laws, which result
from informed assumptions or hypotheses
about the chemical reaction mechanisms.
Ideally, a reaction mechanism and its
corresponding rate laws are found through
conducting rigidly controlled experiments,
where the influence of spatial and time
variations are well known. Sometimes such
experiments are difficult to run, and a
search of the literature or using the rate
laws from similar reactions provides the
first hypothesis. Bench-scale perfectly mixed reactor.

Perfectly mixed or ideal plug flow reactor models are the most effective reactor
types for duplicating and modeling the exact conditions of a rigidly-controlled
experimental study. These virtual experiments are used to study the influence of
various kinetic parameters and other conditions on the behavior of the reacting
system. Then, using parameter estimation, the reaction rate constants for the
proposed reaction mechanisms can be found by comparing experimental and
simulated results. The comparison of these results to other experimental studies
enables the verification or further calibration of the proposed mechanism and its
kinetic parameters.
Modeling a reaction system in a well-defined reactor environment also provides an
understanding of the influence of various, yet specific, operating conditions on the
process, such as temperature or pressure variations. The more knowledge that is
gained about a reacting system or process, the easier it is to model and simulate
more advanced descriptions of these systems and processes.

8|
Investigating Reactors and Systems — Modeling Space Dependency
Once a reacting process or system’s mechanism and kinetic parameters are decided
and fine-tuned, they can be used in more advanced studies of the system or process
in real-world environments. Such studies invariably require full descriptions of the
variations through both time and space to be considered, which, apart from the
reaction kinetics, includes material transport, heat transfer, and fluid flow.

Real world environment.

Depending on assumptions that can (or sometimes must) be made, these
descriptions are done in either 1D, 2D, or 3D, where time dependency can also
be considered if it is of importance.

The temperature isosurfaces throughout a monolith reactor used in a catalytic converter. The surface plot
shows the concentration profile of one of the reactants.

Once again, comparisons between simulation and results, from either the reactor
or system itself, or a prototype of them, should always be done if possible. Models
that involve material transport, heat transfer, and fluid flow often involve generic
material parameters that are taken from the literature or from systems that may be

|9
slightly different, and these may need to be calibrated to improve the accuracy of
the model.
When a model’s accuracy has been ascertained, then it becomes a model that can
be used to simulate the real-world chemical reactor or process under a variety of
different operating conditions. The understanding that results from these models,
as well as the concrete results they provide, go toward developing or optimizing a
chemical reactor with greater precision, or controlling a system with more
confidence.

10 |
Chemical Reaction Engineering Module Interfaces

Figure 2 shows the chemical reaction engineering interfaces available if you are
licensed to the Chemical Reaction Engineering Module. You can use these
interfaces to model chemical species transport, fluid flow, and heat transfer. See
also The Physics Interface List by Space Dimension and Study Type.

Figure 2: The interface list for the Chemical Reaction Engineering Module as shown in the Model Wizard
for a 3D model.

By combining the Chemical Reaction Engineering Module with the CFD, and
Heat Transfer Module, you are also able to incorporate turbulent flow, multiphase
flow, and nonisothermal flow, as well as radiation heat transfer.

C HEMICAL R EACTION AND M ASS T RANSPORT

The Reaction Engineering interface ( ) includes all of the tools required to
simulate chemical reaction kinetics in well-defined environments. It sets up
simulations of reversible, equilibrium, and irreversible reactions in volumes or on
surfaces. You can study the evolution of species concentrations and temperature
in controlled environments described by batch, continuous stirred-tank,
semibatch, and plug flow reactors. Parameter estimation can also be performed,
which then requires a license for the Optimization Module.

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The Chemistry interface ( ) provides libraries of chemical reactions for use by
other physics interfaces. It also provides kinetic expressions for reaction rates,
reaction heat sources, and species transport properties to other interfaces. This
interface is always created when a Reaction Engineering model is exported to a
space-dependent model. As such, it serves as a reaction kinetics and material
property provider to the space-dependent transport interfaces, such as Transport
of Diluted Species.
The Transport of Diluted Species interface ( ) simulates chemical species
transport through diffusion, convection (when coupled to Fluid Flow), and
migration in electric fields for mixtures where one component (that is, a solvent),
is present in excess. It also handles transport in porous media. It supports cases
where either the solid phase substrate is exclusively immobile, or when a gas-filling
medium is also assumed to be immobile.
The Transport of Concentrated Species interface ( ) models chemical species
transport by diffusion, convection, and migration in mixtures where transport
properties, such as diffusion, depend on the composition of the mixture. This
interface supports multicomponent transport models given by Fickian diffusion, a
mixture-average model, as well as the Maxwell-Stefan equations.
The Nernst-Planck Equations interface ( ) includes a migration term, along
with convection and diffusion mass transport, together with an equation that
guarantees electroneutrality. A part from species concentrations, the interface also
solves for the electric potential.
The Nernst-Planck-Poisson Equations interface ( ) is a multiphysics interface
for modeling transport of electrolyte species without the otherwise common
assumption of local electroneutrality. This allows you to simulate charge
separation typically arising close to an electrode surface, where electrolyte ions are
attracted and repelled by unscreened excess charge on the electrode. The charge
separation region, also called the diffuse double layer, normally extends a few
nanometers away from the electrode surface into the electrolyte.
The Electrophoretic Transport interface ( ) is used to solve for the
electrophoretic transport of species in water-based system subject to potential
gradients. The species transported can be any combination of weak and strong
acids and bases, ampholytes, and uncharged species. The interface supports
dissociation equilibria for weak acids, bases, and ampholytes, as well as the water
auto-ionization reaction.
The Laminar Flow interface ( ) under Reacting Flow combines the functionality
of the Single-Phase Flow and Transport of Concentrated Species interface.
The Laminar Flow, Diluted Species interface ( ) under Reacting Flow combines
the functionality of the Single-Phase Flow and Transport of Diluted Species
interface.

12 |
The Reacting Flow in Porous Media, Transport of Diluted Species interface ( )
treats diluted reacting mixtures transported by a free and/or porous media flow.
This multiphysics interface combines the functionality of the Brinkman Equations
and Transport of Diluted Species in Porous Media interface.
The Reacting Flow in Porous Media, Transport of Concentrated Species
interface ( ) treats concentrated reacting mixtures transported by a free and/or
porous media flow. This multiphysics interface combines the functionality of the
Brinkman Equations and Transport of Concentrated Species interface.
The Surface Reactions interface ( ) models reactions involving surface adsorbed
species and species in the bulk of a reacting surface. This interface is used on a
model boundary, and is coupled to a mass transport interface active on a model
domain. The interface can be used together with the Reacting Flow interfaces, and
the Electrochemistry interfaces. The Electrochemistry interfaces require the
addition of one of the Battery Design Module, the Corrosion Module, the
Electrochemistry Module, the Electrodeposition Module, or the Fuel Cell &
Electrolyzer Module. Predefined expressions for the growth velocity of the
reacting surface makes it easy to set up models with moving boundaries.
The Transport of Diluted Species in Fractures interface ( ) is used to model
solute species transported along fracture surfaces where the thickness is very small
compared to the other dimensions. Geometries like these are often hard to mesh.
In this interface the fractures are defined by boundaries in the model geometry,
circumventing the need for a mesh in the thin dimension. The interface allows you
to define the average fracture thickness and also the porosity, for cases when the
fracture is considered to be a porous structure. Different effective diffusivity
models are available for such cases. The interface includes support for transport
due to convection, diffusion, and dispersion, as well as chemical reactions.

S INGLE -P HASE F LOW

The Creeping Flow interface ( ) is used to model flow at very low Reynolds
numbers, in which case the inertial term in the Navier-Stokes equations can be
neglected. Creeping flow, also referred to as Stokes flow, occurs in systems with
high viscosity or small geometrical length scales, for example in microfluidics and
MEMS devices.
The Laminar Flow interface ( ) is used to model flow at low to intermediate
Reynolds’ numbers, and often in combination with mass transport and heat
transfer. The interface solves the Navier-Stokes equations and assumes by default
that a flow is incompressible. This simplifies the numerical scheme and provides
fast and efficient flow simulations. You can also choose to model compressible
flow in which case the density may depend on pressure, composition, and
temperature. The interface supports compressible flow at speeds of less than Mach
0.3.

| 13
Another useful tool is the ability to describe other material properties such as
density and viscosity by entering equations that describe these terms as a function
of other parameters such as material concentration, pressure, or temperature.
Many materials in the material libraries use temperature- and pressure-dependent
property functions.

P OROUS M EDIA AND S UBSURFACE F LOW

The Darcy’s Law interface ( ) is used to model fluid movement through
interstices in a porous medium where a homogenization of the porous and fluid
media into a single medium is done. Together with the continuity equation and
equation of state for the pore fluid this interface can be used to model flows for
which the pressure gradient is the major driving force. The penetration of reacting
gases through a catalytic washcoat or membrane is a classic example for the use of
Darcy’s Law.
Darcy’s law can be used in porous media where the fluid flow pattern is mostly
influenced by the frictional resistance within the pores. Its use is within very slow
flows, or media where the porosity is relatively small. Fluid penetration through
filters and packed beds are applications that are suitable to model with this
interface.
The Brinkman Equations interface ( ) is used to model porous flow when the
size of the interstices is larger; the Brinkman interface extends Darcy's law to
describe the dissipation of the kinetic energy by viscous shear, similar to the
Navier-Stokes equations. The interface includes the possibility to add a
Forchheimer drag term, which simulates viscous drag in very open beds where
turbulent drag becomes important. Forchheimer drag is sometimes called Ergun’s
equations. For very low speed flows or small geometrical length scales, you can
also choose to neglect the inertial term (Stokes flow).
The Free and Porous Media Flow interface ( ) is useful for equipment that
contain domains where free flow is connected to porous media, such as
packed-bed reactors and catalytic converters. It should be noted that if the porous
region is large in comparison to the free fluid region, and you are not primarily
interested in results in the region of the interface, then you can always couple a
fluid flow interface to the Darcy’s Law interface, to make your overall model
computationally cheaper.
As always, the interface gives you direct access to defining, with either constants
or expressions, the material properties that describe the porous media flow. This
includes the density, dynamic viscosity, permeability, porosity, and matrix
properties.

14 |
H EAT T RANSFER
The various Heat Transfer interfaces include Heat Transfer in Fluids ( ), Heat
Transfer in Solids ( ), and Heat Transfer in Porous Media ( ), and account
for conductive and convective heat transfer. These features interact seamlessly and
can be used in combination in a single model.

The Physics Interface List by Space Dimension and Study Type

The table lists the physics interfaces available with this module in addition to those
included with the COMSOL basic license.

PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE

DIMENSION

Chemical Species Transport

Surface Reactions sr all dimensions stationary (3D, 2D, and 2D

axisymmetric models only);
time dependent
Transport of Diluted tds all dimensions stationary; time dependent
Species1
Transport of Diluted tds all dimensions stationary; time dependent
Species in Porous Media
Transport of Diluted dsf 3D, 2D, 2D stationary; time dependent
Species in Fractures axisymmetric
Electrophoretic Transport el all dimensions stationary; stationary with
initialization; time
dependent; time dependent
with initialization
Chemistry chem all dimensions stationary; time dependent

Transport of Concentrated tcs all dimensions stationary; time dependent

Species
Nernst-Planck Equations npe all dimensions stationary; time dependent

Nernst-Planck-Poisson tds+es all dimensions stationary; time dependent;

Equations stationary source sweep;
small-signal analysis,
frequency domain

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PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Reaction Engineering re 0D time dependent; stationary

plug flow
Reacting Flow

Laminar Flow — 3D, 2D, 2D stationary; time dependent

axisymmetric
Laminar Flow, Diluted — 3D, 2D, 2D stationary; time dependent
Species1 axisymmetric
Reacting Flow in Porous Media

Transport of Diluted rfds 3D, 2D, 2D stationary; time dependent

Species axisymmetric
Transport of rfcs 3D, 2D, 2D stationary; time dependent
Concentrated Species axisymmetric
Fluid Flow

Single-Phase Flow

Creeping Flow spf 3D, 2D, 2D stationary; time dependent

axisymmetric
Laminar Flow1 spf 3D, 2D, 2D stationary; time dependent
axisymmetric
Porous Media and Subsurface Flow

Brinkman Equations br 3D, 2D, 2D stationary; time dependent

axisymmetric
Darcy’s Law dl all dimensions stationary; time dependent

Free and Porous Media fp 3D, 2D, 2D stationary; time dependent

Flow axisymmetric
Heat Transfer

Heat Transfer in Fluids1 ht all dimensions stationary; time dependent

16 |
PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Heat Transfer in Solids and ht all dimensions stationary; time dependent

Fluids1
Heat Transfer in Porous ht all dimensions stationary; time dependent
Media
1
This physics interface is included with the core COMSOL package but has added functionality
for this module.

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Tutorial Example: NO Reduction in a Monolithic Reactor

Introduction
This Tutorial Example presents a detailed description of how to set up a model of
a catalytic converter for exhaust gas treatment. The example shows an application
of the modeling strategy, described in the section Chemical Reaction Engineering
Simulations and demonstrates through a series of simulations how an
understanding of the catalytic reactor and its system can be improved. To do this,
it uses a number of the interfaces and features found in the Chemical Reaction
Engineering Module. Transport and thermodynamic properties are provided by
the Thermodynamics feature under Global Definitions.
The system to be modeled is the selective reduction of nitrogen oxide (NO) in a
monolithic reactor placed in the exhaust system of a diesel car. Exhaust gases from
the engine pass through the channels of a monolithic catalytic reactor where, by
adding ammonia (NH3) to this stream, NO is selectively removed through a
reduction reaction. Yet, NH3 is also oxidized in a parallel reaction, and the rates
of the two reactions are affected by temperature as well as composition. This
means that the amount of added NH3 must exceed the expected amount of NO,
while not being so excessive as to release NH3 to the atmosphere.
The goals of the simulations are to find the optimal dosing of NH3, and to
investigate some of the other operating parameters in order to gauge their effects.

Catalytic converters reduce the NOx levels in the exhaust gases emitted by combustion engines.

18 |
Tutorial Modeling Strategy
You may want to revisit the flowchart in Figure 1 to follow the modeling strategy
for this model as described next.
In short, two models, hereafter referred to as Single Channel Model, and 3D
Reactor Model, are set up.
The Single Channel Model is set up in two steps. The first step investigates the
selectivity aspects of the kinetics. This is accomplished by modeling reaction rates
as a function of temperature and relative reactant amounts. A plug flow reactor
with a fixed temperature ramp is used. Reactant molar flow rates are kept constant
as to isolate the effect of temperature and relative reactant amounts. Information
from this model point to the general conditions required to attain the desired
selectivity.
Having a better understanding of the reaction kinetics aids in the development of
a more complex model. So, in the next step, the Single Channel Model is
improved by including variations in flow rates as well as temperature, both as a
result of catalytic activity. This more advanced model reveals the necessary NH3
dosing levels based on the working conditions of the catalytic converter and
assumed flow rate of NO in the exhaust stream.
Last, the 3D Reactor Model of the catalytic converter is set up and solved. Suitable
NH3 dosing level resulting from the Single Channel Model is used. The 3D
Reactor Model, using the Single Channel Model as a base, adds model geometry
that enables modeling of mass transport, heat transfer, and fluid flow. The 3D
Reactor Model thus provides insight and information for optimizing the dosing
levels and other operational parameters.

Chemistry
Two parallel reactions occur in the monolithic reactor. The desired reaction is NO
reduction by ammonia:
4NO + 4NH3 + O2 4N2 + 6H2O (1)

However, ammonia can at the same time undergo oxidation:

4NH3 + 3O2 2N2 + 6H2O (2)

The heterogeneous catalytic conversion of NO to N2 is described by an

Eley-Rideal mechanism. A key reaction step involves the reaction of gas-phase NO
with surface-adsorbed NH3. The following rate equation (SI unit: mol/(m3·s))
has been suggested in Ref. 1 for the desired reduction reaction (Reaction 1):
ac NH3
r 1 = k 1 c NO --------------------------- , (3)
1 + ac NH3

| 19
where
E1
k 1 = A 1 exp  – -----------
 R g T

and
E0
a = a 0 exp  – ----------- .
 R g T

For reaction 2, the reaction rate (SI unit: mol/(m3·s)) is given by

r 2 = k 2 c NH3 , (4)

where
E2
k 2 = A 2 exp  – ----------- .
 R g T

The competing chemical reactions raise the issue of optimal dosing of NH3 to
handle the reduction process. Stoichiometry suggests a 1:1 ratio of NH3 to NO as
a lower limit. It is likely that a stoichiometric excess of NH3 is necessary but, at the
same time, it is important to avoid unnecessarily high levels of NH3 in the gas
stream leaving the catalytic converter.

Single Channel Model

To find the minimal level of NH3 required to reduce the NO present in the
exhaust gas requires a reactor model accounting for changing reactant
concentrations and system temperature.
From a mass transfer point of view, channels of the reactor monolith can be
considered to be independent of each other. Therefore, it is reasonable to perform
initial simulations where a single reactive channel, modeled by nonisothermal plug
flow equations, represents the monolith reactor.

These equations are available withing the Plug flow reactor type in the Reaction
Engineering interface.

20 |
M ODEL E QUATIONS
Assuming steady-state, the mass balance equation for a plug flow reactor is given
by:
dF
---------i = R i , (5)
dV

where Fi is the species molar flow rate (SI unit: mol/s), V represents the reactor
volume (SI unit: m3), and Ri is the species net reaction rate (SI unit: mol/(m3·s)).
The molar flow rate is related to the species concentrations, ci (SI unit: mol/m3),
through the volumetric flow rate, v (SI unit: m3/s):

F i = vc i , (6)

where the volumetric flow rate is given by the average flow velocity, u (SI unit: m/
s), multiplied by the reactor cross-section A (SI unit: m2):

v = uA . (7)

The energy balance for the ideal reacting gas is:

dT
 Fi Cp, i -------
dV
= Q ext + Q , (8)
i

where Cp,i is the species molar heat capacity (SI unit: J/(mol·K)), and Qext is the
heat added to the system per unit volume (SI unit: J/(m3·s)). Q denotes the heat
due to chemical reaction (SI unit: J/(m3·s)):

Q = –  Hj rj ,
j

where Hj the heat of reaction (SI unit: J/mol), and rj the reaction rate (SI unit:
mol/(m3·s)).
The reactor equations are solved for a channel 0.36 m in length with a cross
sectional area of 12.6 mm2. It is assumed that exhaust gas containing 41.1 mmol/
m3 of NO at a temperature of 523 K passes through the channel at 0.3 m/s.
The model is first solved with Equation 5, Equation 6, and Equation 7 for several
different ratios of reactant concentrations (NH3:NO) and with a temperature
ramp along the reactor. The molar flow rates of NH3 and NO are kept constant
throughout the reactor to investigate the temperature impact alone. Thereafter,
Equation 8 is included; that is, nonisothermal conditions due to heat of reaction
are studied.

| 21
Results

R EACTION K INETICS S TUDY

The competing chemical reactions, given by Reaction 1and Reaction 2 above,
raise the issue of optimal dosing of NH3 to handle the reduction process.
Stoichiometry suggests a 1:1 ratio of NH3 to NO as a lower limit. It is likely that
a stoichiometric excess of NH3 is necessary but, at the same time, unnecessarily
high levels of NH3 in the gas stream leaving the catalytic converter need to be
avoided.
Analyzing the kinetics can help identify conditions favoring the desirable
reduction reaction. The Reaction Kinetics Model looks at the reaction rates of the
reduction and oxidation reactions as a function of temperature and relative
amounts of reactants, keeping molar flow rates constant. Figure 3 shows reaction
rates for the reduction reaction (Reaction 1). The curves represent a set of
NH3:NO ratios ranging from 1 to 2. The concentration of NO in the exhaust gas
entering the catalytic converter is known to be 41.1 mmol/m3.

Increasing
NH3:NO

Figure 3: Reaction rates of the NO reduction reaction (r1) as a function of temperature. The NH3:NO
ratio ranges from 1 to 2 and the molar flow rates of NH3 and NO are kept constant throughout the
reactor.

The rate of NO reduction goes through a maximum and falls off at higher
temperatures. Higher NH3 concentration in the gas phase leads to increased levels
of surface-adsorbed NH3, in turn favoring the conversion of gas-phase NO to N2.
This explains the shifts of the rate maximum toward higher temperatures as the

22 |
NH3:NO ratio increases. The decrease in the NO reduction rate at the highest
temperatures is explained by the desorption rate of NH3 from the catalyst surface
becoming faster than the reaction of adsorbed NH3 with gas-phase NO.
According to Equation 4, the ammonia oxidation rate increases with temperature
and NH3 concentration. Figure 4 shows the selectivity parameter, defined as:
r1
S = ----- .
r2

A value greater than one means that NO reduction is favored, while a value of less
than one means NH3 oxidation is the preferred reaction pathway. Clearly the
selectivity for NO reduction drops both with increasing temperature and
increasing NH3:NO ratio.

Increasing
NH3:NO

Figure 4: Selectivity parameter (r1/r2) as a function of temperature. The NH3:NO ratio ranges from 1 to
2.

The Reaction Kinetics study results suggest that preferred working conditions
involve moderate temperatures and relatively low ratios of NH3:NO.

S INGLE C HANNEL M ODEL

To further optimize the dosage of reducing agent, the reactor model needs to
account for changing reactant concentrations and system temperature. For this
purpose, a nonisothermal plug flow reactor serves to simulate the behavior of a
reactive channel.

| 23
The plot in Figure 5 shows the molar flow rate of NH3 as function of position in
the reactor. The set of lines represent NH3:NO ratios ranging from 1 to 2. Under
these conditions results show that a NH3:NO ratio of at least 1.3 is needed to
guarantee that NH3 is available as a reductive agent throughout the entire reactive
channel.

Figure 5: Molar flow rate (mol/s) of NH3 as function of channel volume.

24 |
A plot of the selectivity parameter in Figure 6 confirms that NO reduction is
favored in the entire channel for a dosage level between 1.3 and 1.4.

Figure 6: Selectivity parameter (r1/r2) as a function of channel volume. The NH3:NO ratio ranges from
1.3 to 1.5.

Figure 7 shows the temperature, as well as the conversion of NO, throughout the
single channel reactor. The maximum values for these properties are included. The
highest temperature in the reactor is 532 K for X0 = 1.3, and 533 K for X0 = 1.5.
The conversion of NO is practically 1 (99%) for both X0 values.

| 25
Figure 7: Temperature and conversion as a function of channel volume.

Investigating a 3D Reactor
It is clear from the Single Channel Model that temperature plays a central role in
affecting the optimal dosing of NH3. As the temperature distribution is likely to
vary from channel to channel in a catalytic converter, a full 3D reactor model is
required.

M ODEL G EOMETRY
The monolithic reactor has a modular structure made up of monolith channel
blocks and supporting solid walls. The reactor is 0.36 m long with a 0.1 m radius.

26 |
Each reactive channel has a cross sectional area of 12.6 mm2, and in a channel
block the void fraction is 0.75.

Reactive channel

Channel

Supporting wall
Outlet

x
Inlet

Figure 8: NO reduction chemistry takes place in the channel blocks. Supporting walls hold together the
full reactor structure. Symmetry reduces the modeling domain to one eighth of the reactor geometry.

M ODEL E QUATIONS AND A SSUMPTIONS

In this example a pseudo homogeneous approach is used to model the hundreds
of channels present in the monolith reactor. As no mass is exchanged between
channels, each channel is described by 1D mass transport equations. Furthermore,
fully developed laminar flow in the channels is assumed, such that the average flow
field is proportional to the pressure difference across the reactor. The fluid flow
transports mass and energy only in the channel direction. The energy equation
describes the temperature of the reacting gas in the channels, as well as the
conductive heat transfer in the solid parts of the monolith structure. As the
temperature affects not only the reaction kinetics but also the density and viscosity
of the reacting gas, the energy equation is what really connects the channels in the
reactor structure turning this into a 3D model.

Mass Transport
The mass balances describing transport and reaction in the reacting channels are
given by diffusion-convection equations at steady state:
∇ ⋅ ( – D i ∇ c i ) + u ⋅ ∇c i = R i (9)

| 27
In Equation 9, Di denotes the diffusion coefficient (SI unit: m2/s), ci is the species
concentration (SI unit: mol/m3), and u equals the velocity vector (SI unit: m/s).
The term Ri (SI unit: mol/(m3·s)) corresponds to the species’ rate expression.
Mass transport is only allowed in the direction of the channels, corresponding to
direction of the x-axis in the 3D geometry used in this example. For the diffusive
transport, this is accomplished by setting the y and z-components of the diffusivity
matrix to zero. The pressure-driven flow in the monolith is also defined in the
direction of the x-axis, hereby restricting the convective mass transport to the
channel direction as well. Each monolith channel thus behaves as a 1D plug flow
model with included diffusion. These separate channel models are connected
through the heat transfer equations for the reactor monolith.
Species concentrations are defined at the reactor inlet boundaries:
c = c in .

At the outlet, use the Outflow condition:

n ⋅ ( – D∇ c ) = 0 .

Fluid Flow
Assuming there is fully developed laminar flow in the channels, the average flow
field is proportional to the pressure difference across the reactor. The flow of
reacting gas through the monolith can then be modeled using a Darcy’s Law
interface with the following governing equations:
∇ ⋅ ( ρu ) = 0 (10)

κ
u = – --- ∇p (11)
μ

The monolith is treated as a porous matrix with the effective permeability κ (SI
unit: m2). Similarly to the diffusivity, the y- and z-components of the permeability
matrix are set to zero. The density, ρ (SI unit: kg/m3), and viscosity, μ (SI unit:
Pa·s), of the gas are assumed to be well represented by the temperature-dependent
properties of nitrogen, as only relatively small concentrations of NO and NH3 are
present.
Pressure conditions are set at the reactor inlet and outlet boundaries.

Heat Transfer
A single temperature equation describing the heat transfer in the porous monolith
reactor can be written as:
∂T
( ρC p ) eff ------- + ρ f C pf u ⋅ ∇T = ∇ ⋅ ( k eff ∇T ) + Q (12)
∂t

28 |
For the stationary case this reduces to:
ρ f C pf u ⋅ ∇T = ∇ ⋅ ( k eff ∇T ) + Q (13)

where ρf (SI unit: kg/m3) is the fluid density, Cpf (SI unit: J/(kg·K)) is the fluid
heat capacity, and keff (SI unit: W/(m·K)) is the equivalent thermal conductivity.
Furthermore, u (SI unit: m/s) is the fluid velocity field, which in this model is
calculated in the Darcy’s Law interface, and Q (SI unit: W/m3) is the heat source,
which is due to exothermic chemical reactions:
Q = Q1 + Q2 = – r1 H1 – r2 H2 . (14)

Above, H1 and H2 (SI unit: J/(mol·K)) are the heats of reaction.

The effective conductivity of the solid-fluid system, keff, is related to the
conductivity of the solid, ks, and to the conductivity of the fluid, kf, by:
k eff = Θ s k s + Θ f k f . (15)

In Equation 15, Θs denotes the solid material’s volume fraction, which is related to
the volume fraction of the fluid Θf by:
Θf + Θs = 1 . (16)

Equation 13 is the equation set up by the Heat Transfer interface for a fluid
domain. For the supporting walls in the reactor, only heat transfer by conduction
applies:
– ∇ ⋅ ( k s ∇T ) = 0 , (17)

where ks (SI unit: W/(m·K)) is the thermal conductivity for the solid walls.
The temperature is specified at the reactor inlet walls boundary:
T = T0 ,

and the Inflow condition; that is,

– n ⋅ q = ρΔHu ⋅ n

is used at the inlet of the geometry. ΔH (SI unit: J/(kg)) is the sensible enthalpy.
At the outlet, use the Outflow condition:
n ⋅ ( k∇T ) = 0 .

For the reactor walls, the heat flux through the boundaries is given by
q m ⋅ n = h ( T – T amb ) ,

| 29
where h (SI unit: W/(m2·K)) denotes the heat transfer coefficient, and Tamb (K)
equals the ambient temperature.
As mentioned, the temperature affects not only reaction kinetics but also the
density and viscosity of the reacting gas. In this way the heat transfer equation
connects the channels in the reactor structure.

Thermodynamic and Transport Properties

Accurate thermodynamic data is required as input to energy balance equations,
both in the Single Channel Model (plug flow model, (Equation 8)) and the 3D
Reactor Model (Equation 13). In addition to thermodynamic properties, the
model equations also require transport properties to describe the space-dependent
reactor model.
The Thermodynamics feature provides all necessary properties for the simulation.
Different models are available for thermal and transport property calculations (see
Thermodynamic Models and Theory). In this system, thermodynamic properties are
calculated based on the ideal gas law while transport properties such as diffusivity,
viscosity, and thermal conductivity are calculated from Fuller Schettler Giddings,
Brokaw, and Kinetic Theory, respectively.

Results
The plot in Figure 9 shows the conversion of NO in the monolith channel blocks
for the optimal NH3:NO ratio of 1.35. The average conversion at the outlet is 97%
not seen in the plot, see Average Conversion and Maximum Temperature section on
how to derive these values). This is somewhat lower than the 99% conversion
predicted by the single channel model. The isosurfaces in the plot show how a

30 |
channel’s performance depends on its position in the reactor, clearly pointing to
the 3D nature of the problem.

Figure 9: Isosurfaces showing the conversion of NO in the reactor. Fluid flow from left to right.

The individual channels, although they do not exchange mass, are connected
through the temperature distribution in the reactor. The temperature affects both

| 31
the flow velocity of the reacting gas as well as the reaction rates. Cross sections of
the reactor temperature are shown in Figure 10.

Figure 10: Temperature distribution in cross sections of the reactor. Fluid flow from left to right.

The exothermic reactions increase the temperature in the central parts of the
reactor, while the temperature in the outer parts is decreased through heat loss to
the surroundings. The maximum temperature calculated for the 3D reactor is
544 K (see Average Conversion and Maximum Temperature section on how to derive
this value), which is about 10 K higher than for the single channel model. The
effect of the relatively high thermal conductivity of the supporting walls is clearly
visible.
A seen from the kinetic analysis in the Single Channel Model, elevated
temperatures have a detrimental effect on the selectivity, leading to ammonia
getting oxidized (Reaction 2) rather than be consumed in the NO reduction
reaction (Reaction 1). The connection between temperature and selectivity is

32 |
clearly seen in the final plot in Figure 11, where both S and T are shown. Here,
symmetry is used to visualize the full monolithic structure.

Figure 11: Selectivity and temperature in slices throughout the monolith reactor. Fluid flow from left to
right.

Figure 11 shows that channels in the relatively cold region near the reactor outer
surface display high selectivity throughout, whereas channels in the region close
to the center see selectivity falling off comparatively fast. The fact that r1/r2 is
greater than 1 throughout the whole reactor means that the desired reduction
reaction is favored. The inclusion of Darcy’s velocity field aids in showing the flow
direction through the reactor.
The information from this 3D model can also be used to investigate other aspects
of this reacting system. For example, the results can be compared to other results
from prototypes or even real monolith reactors, and material properties, such as
the permeability constant, can be fine-tuned. Different operating conditions, such
as when the automobile accelerates and decelerates, can be simulated. Alternative
catalysts and designs can also be investigated.

| 33
Summary
The Chemical Reaction Engineering Module is used to perform two different
levels of analysis concerning the reduction of NO in a monolithic reactor:
• Single Channel Model — With a simple plug flow reactor model explore the
reaction kinetics and narrow down the conditions that promote selectivity
toward NO reduction. The tuning of the dosage is improved by performing
the modeling in two steps; that is, by first isolating the impact of
temperature and reactant ratio.
• 3D Reactor Model — testing the reactor operating conditions in a full 3D
reactor representation, noting the space-dependent effect due to coupling
between monolith channels.
A reactant ratio NH3:NO of approximately 1.35 is found to be close to optimal
under the investigated conditions. This ratio leads to minimal waste of ammonia
without limiting the NO reduction chemistry. It also favors the selectivity for NO
reduction while at the same time restricting the possible heat evolved through the
chemical reactions. This in turn helps control the temperature in the reactor, again
favoring the NO reduction.
The modeling strategy used in this example has several advantages. Starting with
fast simulations using easy to set up models makes it easier to identify and narrow
down the process condition envelope before moving to more advanced and
computationally demanding models. The sequential modeling approach also helps
to identify when and how effects such as temperature dependency and space
dependency come into play. This deepened system understanding leads to efficient
model setup and solution strategies. Going from perfectly mixed conditions to full
space dependency in 3D also puts you in the position to decide on what level of
detail that is needed for the particular system.

References
1. G. Shaub, D. Unruh, J. Wang, and T. Turek, “Kinetic analysis of selective
catalytic NOx reduction (SCR) in acatalytic filter”, Chemical Engineering and
Processing, vol. 42, p. 365–71, 2003.

Note on the Models

The following step-by-step instructions guide you through the process to set up
and solve the two models that simulate the catalytic reduction of NO in a
monolith reactor. The first model, Single Channel Model, makes use of a simple
plug flow reactor model. The second model, 3D Reactor Model, accounts for the
full 3D monolithic reactor, coupling mass transport to heat transfer and fluid flow.

34 |
As an option to first build the Single Channel Model, you can open the completed
model file for the Single Channel Model and proceed directly with the setup of
the 3D Reactor Model. See Modeling Instructions: 3D Reactor Model for further
details.
Both the Single Channel Model and the 3D Reactor Model are available in the
Application Libraries, see monolith_kinetics.mph and monolith_3d.mph,
respectively.
Here follows the step-by-step instructions guide to how to build the Single
Channel Model and the 3D Reactor Model.

| 35
Modeling Instructions: Single Channel Model

By following these steps you will be able to set up the Single Channel Model.

Model Wizard

Note: These instructions are for the user interface on Windows but apply, with
minor differences, also to Linux and macOS.
1 To start the software, double-click the COMSOL icon on the desktop. When
the software opens, choose to use the Model Wizard to create a new COMSOL
model, or choose Blank Model to create one manually. For this tutorial, click
the Model Wizard button.
If COMSOL is already open, start the Model Wizard by choosing New
from the File menu and then click Model Wizard .
The Model Wizard guides you through the first steps of setting up a model. The
next window lets you choose the dimension of the modeling space.
2 In the Select Space Dimension window click the 0D button.
3 In the Select Physics tree, expand the Chemical Species Transport node. Then
double-click Reaction Engineering (re) to add it to the Added physics list.
Optionally, right-click and choose Add Physics .
4 Click Study . In the Select Study tree, under Preset Studies for Selected
Physics Interfaces, select Stationary Plug Flow .
5 Click Done .

D ef i n i t i o n s — P ar am et er s an d V ar ia b l es

Start by importing a set of global parameters defining the process conditions for
the monolith reactor, including for example the dimensions of the reactive
channels, the flow rate of the incoming gas and the inlet temperature. Then
import the variables for model specific expressions defining rate constants and the
selectivity parameter S.
Note: The location of a file is based on the installation. For example, if the
installation is on your hard drive, the file path might be similar to C:\Program
Files\COMSOL56\applications\.

36 |
P ARAMETERS
1 In the Home toolbar, click Parameters and choose Parameter 1 .
Note: On Linux and macOS, the Home toolbar refers to the specific set of
controls near the top of the Desktop.
2 In the Settings window under Parameters, click the Load from File button .
3 Browse to the file monolith_kinetics_parameters.txt in the application
library folder on your computer,
Chemical_Reaction_Engineering_Module\Tutorials. Double-click to
add or click Open.
The parameters from the txt-file are added to the table.

V ARIABLES
1 In the Home toolbar, click Variables and choose Local variables (or in the
Model Builder under Component 1, right-click Definitions , and choose
Variables ).
2 In the Settings window for Variables window locate the Variables section.
3 In the table, enter these settings:

NAME EXPRESSION UNIT DESCRIPTION

S re.r_1/re.r_2 Selectivity
a a0*exp(-E0/(R_const*re.T)) m3/mol Concentration
correction

| 37
Here, re.r_1 is the variable name for the reaction rate for Reaction 1, see Equation 3.
Since the reactions have not yet been added to the model, the expression for S is
shown in yellow, indicating unknown variables. One way to find the generated
variable names is shown in Equation View below.
Also notice the inbuilt function that automatically recognizes and adds the unit
for variable a.

T h e r m o d yn a m i c S y s t e m

Next, create a Thermodynamic System that includes all thermodynamic properties

needed in the simulation of the reacting system. Included with the system comes
the ability to set up predefined expressions for transport and thermodynamic
properties. The transport expressions, for instance the species diffusivity
coefficients, are used in the 3D reactor model described further on.
The thermodynamic properties are automatically coupled to the Reaction
Engineering interface. The Thermodynamics feature is available under Global
Definitions.
1 In the Reaction Engineering toolbar, click Thermodynamics and choose
Thermodynamic System.
This opens the Thermodynamic System Wizard which is used to define a system,
including phase and species, and to set up thermodynamics and transport
properties models.
2 In the first step in the wizard, keep Gas as the Selected system. Click Next
in the window toolbar.

38 |
3 In Select Species window, type the name of the
gas species that are present in the reactor system
and Add them to the Selected species table.
Click Next .
4 In the Select Thermodynamic Model, keep Ideal
gas as Gas phase model.
As an option, check the Advanced options check
box to select transport properties for later use in the
space-dependent model. For now, keep the default
selection by leaving the box unchecked.
5 Click Finish .
In the Settings window it is possible to review all the
properties of the created Gas System .

Reaction Kinetics

Now define the chemical reactions. First, enter the reaction formula for NO
reduction. The Reaction Engineering interface automatically interprets the
reaction formula and suggests a reaction rate based on the mass action law (that
is, stoichiometry).

R EACTION 1
1 In the Reaction Engineering toolbar, click
Reaction (or in the Model Builder window, under
Component 1, right-click
Reaction Engineering (re) and choose
Reaction ).
2 In the Settings window for Reaction under Reaction
Formula, type 4NO+4NH3+O2=>4N2+6H2O in the
Formula text field.

| 39
3 Click Apply to generate the Reaction node as well as one Species node for each
of the species in the Reaction Formula.

Notice that, there being several ways to balance this formula, the button Balance
is not applicable in this case.
4 In the Model Builder click the 1: 4NO+4NH3+O2=>4N2+6H2O node .
In this example, replace the automatically generated reaction rate expression with
the rate expression known from the literature.
5 Locate the Reaction Rate section. From the Reaction Rate list choose User
defined.
6 In the Reaction rate (rj) text field type re.kf_1*re.c_NO*a*re.c_NH3/
(1+a*max(re.c_NH3,0[M])). The max operator in the denominator helps
avoid negative concentrations, and [M] is the unit molar.

In the next step, update the reaction order to avoid unit errors.
7 Under Volumetric overall reaction order, enter a Forward value of 1. This
implies a rate constant with the unit 1 / s.
Enter the Arrhenius parameters for the temperature dependent rate constant used
for the reaction.
1 Under Rate Constants select the Use Arrhenius
expressions check box.
2 Enter the Arrhenius parameters for the reaction.
Since a default irreversible reaction is used, only the
Forward reaction parameters are needed.
- In the Forward frequency factor (Af) text field,
type A1.
- In the Forward activation energy (Ef), type E1.

In the same fashion, now define the reaction for ammonia oxidation.

40 |
R EACTION 2
1 In the Reaction Engineering toolbar, click Reaction .
2 In the Settings window for Reaction, locate the Reaction Formula section. Type
(or copy and paste) NH3+O2=>N2+H2O in the Formula text field.
3 Click Apply.
4 Click Balance in the upper-right corner of the Reaction Formula section.
This reaction can be balanced since there is only one solution to the balancing
problem.
5 Locate the Reaction Rate
section. From the Reaction Rate
list choose User defined. Type
re.kf_2*re.c_NH3 in the
Reaction rate (rj) text field.
Change Forward reaction order
to 1.
6 Locate the Rate Constants section. Select the Use
Arrhenius expressions check box.
- In the Af text field, type A2.
- In the Ef text field, type E2.

Now that the reactions and kinetics settings are set,

use Equation View to check what variable names
that were generated.

Equation View
1 In the Model Builder window, click Show More Options .
2 Under Physics, check Equation View check box. Click OK.
3 In the Model Builder window, expand the 1: 4NO+4NH3+O2=>4N2+6H2O
node . Click Equation View. Scroll through the Variables list to see the
generated variable names, their expressions, units and descriptions.

After setting up the reaction kinetics, define the suitable reactor model where the
reactions take place. Using the Reaction Engineering node you can choose one of
the predefined reactor types. Since you are planning to set up a simple channel

| 41
model, having chosen the Stationary Plug Flow study type previously, choose the
Plug flow reactor.

Reactor Model — Kinetics Study

As mentioned in the Tutorial Modeling Strategy, the

first step is to investigate the selectivity aspects of the
kinetics. This is accomplished by modeling reaction
rates as a function of temperature and relative reactant
amounts. A plug flow reactor with a fixed
temperature ramp is used. Reactant molar flow rates
are kept constant as to isolate the effect of
temperature and relative reactant amounts.
1 In the Model Builder, click the Reaction
Engineering (re) node.
2 In the Settings window under Reactor Settings,
from the Reactor type list choose Plug flow.
Now couple all species in Reaction Engineering to
the corresponding species in the created
Thermodynamic System.
3 Locate the Mixture Properties section. Select the Thermodynamics check box.
4 Locate the Species Matching section. In the table, match the species in Reaction
Engineering to the same species in Thermodynamics. The table will look like
this after matching:

Since the volumetric flow rate should be kept constant in this particular example,
choose to compute the pressure from the ideal gas law.
5 In the Mixture Properties section, choose Ideal gas law from the Reactor
pressure list.
The following steps allow you to study the reaction rate for fixed reactant
concentrations, solely as a function of temperature. First, use the independent
variable V (reactor volume, written re.Vr) to set up a temperature ramp between

42 |
500 K and 750 K. Then, after defining initial values, lock the concentrations of
reactant NO and NH3 and add a Parametric sweep feature.
6 Locate the Energy Balance section. From the list, choose Exclude.
7 In the Temperature (T) text field, type 500[K]+250[K/m^3]*re.Vr.
8 Locate the Reactor section. Find the Mass balance subsection. In the
Volumetric flow rate (v) text field, type vrate, previously defined in the
Parameters section.

I NITIAL V ALUES
In the next steps, define inlet values for the reactor.
1 In the Model Builder window, under Reaction Engineering click
Initial Values 1 .
2 In the Settings window for Initial Values, locate the Volumetric Species Initial
Values section.
3 In the table enter the following settings:

SPECIES MOLAR FLOW RATE (MOL/S)

H2O F_H2O_in
N2 F_N2_in
NH3 F_NH3_in
NO F_NO_in
O2 F_O2_in

S PECIES : NO AND S PECIES : NH3

Next, lock the concentrations of reactants NO and NH3 to only investigate the
impact of the temperature and reactant ratios on the inlet reaction rates.
1 One at a time in the Model Builder, click the Species: NO and the
Species: NH3 nodes. In each Settings window expand the Species
Concentration/Activity section.
2 Select the Constant concentration/activity check box in these sections to set the
species concentration constant.

| 43
Stud y — Reaction Kinetics

Add a Parametric Sweep feature to solve the model for a set of NH3:NO ratios.

P ARAMETRIC S WEEP
1 In the Study toolbar click Parametric Sweep .
2 Under Study Settings, click the Add button below the table. In the
Parameter name column, choose X0 (Ratio NH3 to NO at inlet).
3 Start with a quite wide range and narrow down the optimal X0 values later. In
the Parameter value list column, type range(1,0.2,2) to solve for ratios
ranging from 1 to 2.

It is good practice to tighten the default solver tolerances and make sure that the
solution plots do not change between consecutive runs. Both the relative and
absolute tolerance should be tightened. In this case the relative tolerance needs to
be reduced to 1e-7.

S TEP 1: S TATIONARY P LUG F LOW

1 In the Model Builder under Study 1, click Step 1: Stationary Plug Flow .
2 In the Settings window locate the Study Settings section. From the Tolerance
list, choose User controlled and type 1e-7 in the Relative tolerance text field.
3 In the Study toolbar click Compute .
All the solutions generated by pressing Compute in the Study interface are saved
and can be copied and modified. This enable easy post-processing of the results,
since several different case studies, within the same model, can be saved and
compared.

Results — Reaction Kinetics

When a model is re-computed many times with small or large sets of changes in
the conditions, it is advisable to save the solution after each computation.

44 |
P ARAMETRIC S OLUTIONS
1 In the Model Builder under Study 1>Solver Configurations, right-click
Parametric Solutions 1 and from the Solution menu choose Copy .
2 In the Settings window for the copied node, type Kinetics in the Label text
field (or press F2 to rename the node). The solution named Kinetics is now
available for further post-processing.
Follow these steps to generate the first figures (Figure 3 and Figure 4) displaying
the results for the single channel model with the fixed reactant ratios and
temperature ramp.

R EACTION RATE - F IGURE 3

1 Under Results click the Molar Flow Rate (re) node. Type Reaction rate
in the Label text field in the Settings window to change the name of the plot
group.
2 Under the Data section of the Reaction rate node, from the Dataset list,
choose the saved solution Study 1/Kinetics.
3 The title is removed to reduce the information in the plot. Click to expand the
Title section and in the Title type list choose None.
4 Locate the Plot Settings section. Ensure the x-axis label check box is ticked.
5 In the associated text field, type Temperature (K).
6 Scroll down to the Legend section and choose Upper left in the Position list.
7 In the Model Builder window, expand the
Reaction rate node and click Global 1 .
8 In the Settings window locate the y-Axis Data
section. Click Replace Expression and either
search or choose re.r_1 under Component
1>Reaction Engineering. Double-click the
expression.
9 In the x-Axis Data section choose Expression from
the Parameter list. Type re.T in the Expression
text field.
10Find the Coloring and Style section and expand it.
Type 2 in the Width text field.
11Expand the Legends section. In the Include
subsection click to clear the Expression check box.
12Click Plot to generate Figure 3. Click the Zoom
Extents button in the Graphics toolbar.

| 45
S ELECTIVITY - F IGURE 4
The most efficient way to create a similar plot is to duplicate an existing one.
1 In the Model Builder window, right-click the Reaction rate node and
choose Duplicate .
2 This plot is intended to display the selectivity. In the Settings window for the
duplicated node, type Selectivity in the Label text field.
3 Locate the Legend section and choose Upper right in the Position list.
4 Expand the Selectivity node and click Global 1 .
5 In the Settings window, locate the y-Axis Data section. Click
Replace Expression and under Component 1>Definitions>Variables
choose S - Selectivity by double clicking.
6 In the Settings window for Global, click Plot to generate Figure 4. Click the
Zoom Extents button in the Graphics toolbar.

Single Channel Model

With the results from the reaction kinetics study (Figure 3 and Figure 4) you now
have an idea of how the reaction kinetics behave. With this information, continue
the monolith system investigation by setting up a single channel model where the
effects of generated heat, as well as varying reactant concentrations, are studied.

E NERGY B ALANCE
1 In the Model Builder under Component 1 (comp1), click the
Reaction Engineering (re) node.
2 In the Settings window, locate the Energy Balance section. Choose Include.
3 Replace the expression in the
External heating or cooling (Q) text field with
(T_amb-re.T)*UA. Remember to use Equation
View to find the variable names.

I NITIAL V ALUES
The inlet temperature needs to be defined as well.
1 In the Model Builder under Reaction Engineering, click Initial Values I .
2 In the Settings window for Initial Values, locate the General Parameters section.
Type T_in in the Inlet temperature (T0,in) text field.

46 |
S PECIES : NO AND S PECIES : NH3
The concentration within the reactor should be
variable in the Single Channel Model.
1 In the Model Builder, one at a time click the
Species: NO and Species: NH3 nodes.
2 Click to clear the Constant concentration/activity
check box in the Species Concentration/Activity
section.

Stud y — Broad Parametric Sweep

Solve the model with the new reactor settings. The Parametric Sweep settings are
active and will be applied.

S TEP 1:S TATIONARY P LUG F LOW

1 In the Model Builder under Study 1, click Step
1: Stationary Plug Flow .
2 In the Settings window locate the Study Settings
section. In the Output volumes text field, type 0[m^3]
L*A to solve the model for a tube reactor with the
length L [m] and cross section area A [m^2]. These two variables were added
in Parameters.
3 Click Compute .

Re sults — Fig u re 5

P ARAMETRIC S OLUTIONS
First save the current solution.
1 In the Model Builder under Study 1>Solver Configurations, right-click
Parametric Solutions 1 . From the Solution menu, choose Copy .
2 In the Settings window for the copied node, type Nonisothermal in the Label
text field.
Follow these steps to generate Figure 5.

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M OLAR F LOW R ATE - F IGURE 5
1 In the Model Builder window, under Results click the Molar Flow Rate (re)
node. Type the plot group name, Molar flow rate NH3, Nonisothermal in
the Label text field.
2 In the Settings window, under the Data section, choose the saved solution
Study 1/Nonisothermal from Dataset list.
3 The title can be removed. Click to expand the Title section and in the Title type
list choose None.
4 Locate the Plot Settings section. Select the y-axis label check box.
5 Type Molar flow rate NH₃ (mol/s) in the associated text
field.
6 In the Model Builder window, expand the Molar flow rate NH3,
Nonisothermal node, then click Global 1 . In the Settings window, click
Replace Expression in the y-Axis Data section. Under Component
1>Reaction Engineering choose re.F_NH3.
7 Find the Coloring and Style section and expand it. Type 2 in the Width text
field.
8 Expand the Legends section. In the Include subsection click to clear the
Expression check box.
9 Click Plot in the 1D Plot Group toolbar to generate Figure 5.

Stud y — Narrow P arametric Sw eep

Use the results presented in Figure 5 to refine the range of reactant ratios X0 to
solve the model for.

P ARAMETRIC S WEEP
1 In the Model Builder window, under Study 1 click Parametric Sweep .
2 In the Settings window, locate the Study Settings section. Change the text in
the Parameter value list to range(1.3,0.1,1.5).
3 In the Home toolbar, click Compute .

Results — Figure 6

First save the current solution.

48 |
P ARAMETRIC S OLUTIONS
1 In the Model Builder under Study 1>Solver Configurations, right-click
Parametric Solutions 1 . From the Solution menu, choose Copy .
2 In the Settings window for the copied solution, type Nonisothermal 2 in the
Label text field.

S ELECTIVITY - F IGURE 6
Follow these steps to generate the results in Figure 6.
1 Under Results click the Temperature (re) node. In the Settings window,
type Selectivity, Nonisothermal in the Label text field.
2 Under the Data section from the Dataset list, choose the saved solution
Study 1/Nonisothermal 2.
3 Click to expand the Title section. From the Title type list choose None.
4 Move the legend box by choosing Middle right in the Position list in Legend
section.
5 In the Model Builder expand the plot group node and click Global 1 .
6 In the Settings window in the y-Axis Data section click
Replace Expression . Either search for or choose S-Selectivity from
the Component 1>Definitions>Variables menu.
7 Expand the Coloring and Style section. Type 2 in the Width text field.
8 Locate the Legends section. In the Include subsection click to clear the
Expression check box.
9 Click Plot to generate Figure 6.
In the last steps of the Single Channel Model tutorial, create Figure 7, displaying
temperature and conversion as a function of reactor volume. Graph markers are
added to display the maximum temperature and conversion reached in the reactor.

T EMPERATURE - F IGURE 7
1 In the Model Builder window, under Results, right-click the
Selectivity Nonisothermal node and choose Duplicate .
2 In the Settings window of the duplicated node, type Temperature,
Nonisothermal in the Label text field.
3 Expand the plot group node and click the Global 1 node. In the Settings
window, click Replace Expression in the y-Axis Data section. Under
Component 1>Reaction Engineering choose re.T-Temperature-K.
Now add the Graph Markers for the temperature data.

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1 Click Plot in the 1D Plot Group toolbar.
2 Right-click Global 1 and choose Graph Marker.
3 In the Settings window for Graph Marker, locate the Display section.
4 From the Display list, choose Max.
5 Locate the Text Format section. In the Display precision text field, type 3.
6 Select the Include unit check box.

C ONVERSION - F IGURE 7
1 Right-click Global 1 and choose Duplicate .
2 In the Settings window for Global, locate the y-Axis Data section.
3 Click Clear Table .
4 In the table, enter the expression for conversion, and add a description in the
Description field. The table will look like this:

Now add the Graph Marker for conversion.

1 In the Model Builder window, expand the Global 2 node, then click Graph
Marker 1.
2 In the Settings window for Graph Marker, locate the Text Format section and
clear the Include unit check box.
3 Click to expand the Coloring and Style section. From the Anchor point list,
choose Lower right.
We have now added temperature and conversion data, as well as Graph Markers
to the plot group called Temperature, Nonisothermal. In the last few steps,
exclude some of the data curves from the plot group, add a secondary y-axis and
change line styles.
1 In the Model Builder window, click Temperature, Nonisothermal.
2 Locate the Data section in the Settings window and choose From list in the
Parameter selection X0 list
3 In the Parameter values (X0) list, choose 1.3 and 1.5.

50 |
4 Locate the Plot Settings section. Select the Two y-axes check box.
5 In the table, select the Plot on secondary y-axis check box for Global 2.
6 In the Temperature, Nonisothermal toolbar, click Plot .
7 Click Global 2 and locate the Coloring and Style section in the Settings window.
8 From the Color list, choose Cycle (reset).
9 Find the Line style subsection. From the Line list, choose Dashed.

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Modeling Instructions: 3D Reactor Model

Note: The model so far is available from the Application Libraries under the
folder Tutorials. As an option, you can open the model file
monolith_kinetics.mph from this folder and continue with the following
step-by-step instructions.
The 3D Reactor Model aims to make use of several inbuilt thermal and transport
properties. This needs first to be accounted for in the Reaction Engineering ( )
interface.

Global Definitions — Parameters

The optimal NH3:NO ratio found in the Single Channel Model, i.e.
monolith_kinetics.mph, is utilized in this model. Start by changing this value
in the Parameters section.
1 In the Model Builder window, expand Global Definitions and click
Parameters 1 .
2 In the Parameters table type 1.35 in the Expression column for the parameter
X0. Replace the existing value.
At the end of the parameter list, add the following new parameters:
3 The 3D model will also make use of a porosity parameter (the gas phase volume
fraction) in several locations. Add the parameter por, with the value 0.75 and
the description Gas phase volume fraction.
4 Add Density of nitrogen at T_in as a parameter d_N2_in with a value of
0.65[kg/m^3]. This value is extracted from the density function for nitrogen
at Thermodynamics (see Species Property).
5 Add parameter A_in for Inlet cross sectional area with the value
3359.9[mm]. (For information: The value for this parameter can be calculated
by selecting the inlet area from the Measure feature under Geometry .
This can be done when the Geometry is defined.)
6 Add parameter M0_in, with value of v_av*por*A_in*d_N2_in and the
description Mass flow inlet.

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Preparing to Go 3D

The 3D Reactor Model uses the 0D Single Channel Model as a base. Before
connecting the 0D model to the other physics interfaces, as well as a reactor
geometry, implement the assumption that nitrogen, being in excess, works as a
solvent. This simplifies computation of several transport properties considerably.
After that, generate a space-dependent model.

N2 AS SOLVENT
1 In the Model Builder window, expand the Reaction
Engineering node under Component 1.
2 Click Species: N2 .
3 In the Settings window locate the Species Type
section. Choose Solvent from the Species type list.

G ENERATE S PACE -D EPENDENT M ODEL

The Generate Space-Dependent Model feature
creates a link between the plug flow single channel
model and the full 3D reactor model. This enables
transfer of reaction kinetics, thermodynamics, and
transport properties, set up in the Reaction
Engineering interface, to the physics interfaces
describing space and time-dependent systems. The
reaction kinetics are all collected in a Chemistry
interface within the 3D model.
1 In the Reaction Engineering toolbar click
Generate Space-Dependent Model (or
right-click Reaction Engineering (re) and
choose it from the menu).
2 In the Physics Interfaces section:
- From the Chemical Species Transport list,
choose Transport of Diluted Species in
Porous Media: New.
- From the Fluid flow list, choose Darcy’s Law: New.
- From the Heat transfer list, choose Heat Transfer in Porous Media: New.

3 Locate the Space-Dependent Model Generation section. Click Create/Refresh.

A 3D (the default in Component Settings section) component setup is initiated.

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The new 3D component, called Component 2, appears in the Model Builder
window. A Chemistry node is automatically created. It includes the kinetic,
thermal, and transport properties setup in the Reaction Engineering interface. If
necessary, changes can be made directly to this node.

Note: In addition to the three physics interfaces that were added with the
Generate Space-Dependent Model feature, additional interfaces can be added by
clicking Add Physics in the Home toolbar.

Setting up the 3D Model

First rename the Component node.

C OMPONENT 2
1 In the Model Builder click Component 2 (comp2).
2 Type 3D Model in the Label text field.
Now define some variables that will be needed.

V ARIABLES
1 In the Home toolbar, click Variables and choose Local variables. Optionally,
go to the Model Builder window, expand the 3D Model node, right-click
Definitions , and choose Variables .
2 In the Settings window for Variables, locate the Variables section.
3 In the table, enter the following settings:

NAME EXPRESSION UNIT DESCRIPTION

S chem.r_1/chem.r_2 Selectivity
3/
a a0*exp(-E0/(R_const*chem.T)) m Concentration
mol correction

G EOMETRY
Use the Geometry node to import a file with the reactor geometry. Symmetry
reduces the modeling domain to one eighth of the full monolith.

54 |
1 In the Geometry toolbar click Insert Sequence .
2 Browse to the file monolith_3d_geom_sequence.mph in the application
library folder on your computer,
Chemical_Reaction_Engineering_Module\Tutorials. Double-click to
add.
Note: The location of a file is based on the installation. For example, if the
installation is on your hard drive, the file path might be similar to C:\Program
Files\COMSOL56\applications\.
3 In the Geometry toolbar, click Build All .

Note: In this step-by-step, focusing on the Chemical Reaction Engineering

Module, all geometry settings are already done. For information, a central part of
the model setup consists of assigning features to domains and boundaries of the
model geometry. The use of Explicit Selections features added to the
geometry makes this process more efficient. The imported geometry sequence
contains eight predefined Explicit Selection nodes. The names and the selected
entities of these selections are seen in the table below.

NODE NAME DOMAINS OR BOUNDARIES SELECTED

Supporting walls domain 1 only

Channel blocks domains 2, 3, 4, 5, and 6

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 NODE NAME DOMAINS OR BOUNDARIES SELECTED

Inlet boundaries 4, 9, 13, 19, and 23

Outlet boundaries 30, 31, 32, 33, and 34
Symmetry boundaries 2, 3, 6, 8, 15, and 18
Inlet walls boundary 1 only
Outlet walls boundary 29 only
Reactor surface boundary 27 only
Domains or boundaries can be assigned to the Explicit nodes by clicking in the
geometry. This adds the identification number of the domain or boundary to the
Input Entities list. To remove a selection, click again to toggle.
Apart from the above Explicit Selections nodes, the sequence also contains a
Union Selection , Inlet end, that contains all boundaries on the inlet. This
selection is defined as the union of the Inlet and the Inlet wall selections.
More Selection nodes are available from the Selections menu in the Geometry
toolbar.

Mate rials

The next step is to specify material properties for the model. Ready-to-use
materials can be selected from the available libraries or generated from
Thermodynamics. In this model, first generate a material node for nitrogen
(solvent) from our Gas System, under Thermodynamics. After that, generate the
solid monolith material. Both these materials are then used to create a Porous
Material.
The created materials are assigned to the relevant selections in the geometry. This
allows the physics interfaces in these selections to access the material properties.

T HERMODYNAMICS
1 In the Model Builder, under Global Definitions , locate
Thermodynamics > Gas System .
2 Right-click on Gas System and choose Generate Material .
This opens the Generate Material wizard which consists of several steps to create
a Material node from our property package.
3 In Select Phase window, choose Gas (default) and click Next .
4 In Select Species window, Add all to the Select species table (default).

56 |
5 In Material composition section, set the mole fraction of nitrogen as 1 and 0 for
others.
6 Click the mass fraction button.
7 Click Next in the window toolbar.
8 In the Select Properties window, choose Diffusion
coefficient at infinite dilution, and click Add Selected
.
9 In the Select solvent subsection, choose nitrogen
from the Select solvent list. Click Next .
10In Define Material window, choose Global from the
Component list. This adds the material to the global
Material node and thus makes it accessible for the
Porous Material feature.
11From the Function type list, choose Interpolation.
This creates interpolation functions for the material
properties, which provides faster property
evaluations.
12Set the Temperature upper bound (High) to 673.
Click Finish .

M ATERIALS

Gas
1 In the Model Builder, expand the 3D Model>Materials node, then click Gas:
ammonia(0)-nitrogen(1)-nitrogen oxide(0)-oxygen(0)-
water(0) .
2 In the Settings window, change the Label to Gas: Nitrogen.
Next, create a user-defined material and associate it with the supporting walls.

Solid
1 In the Materials toolbar, click Blank Material .
2 In the Model Builder window, expand the Material 1 node, then click Basic
(def).

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3 In the Settings window for Property
group, locate the Output Properties
section. Click Select Quantity
below the table.
4 In the Physical Quantity dialog box,
type density in the text field and
click Filter . Select Density (kg/
m^3). Click OK.
5 Perform the same action for the properties heatcapacity (choose Heat
capacity at constant pressure (J/(kg*K)) and thermalconductivity (choose
Thermal conductivity (W/(m*K)).
6 Add the expressions to the Output Properties section. Type 2970[kg/m^3] for
the density, 975[J/kg/K] for the heat capacity, and 35[W/m/K] for the thermal
conductivity.
7 In the Model Builder window, right-click Material 1 and choose Rename.
8 In the Rename Material dialog box, type Solid: Monolith Material in the
New Label text field.
9 Click OK.
In the next stage of the modeling process, add a Porous Material that consists of
the two materials that were just defined.

Porous Material
1 In the Materials toolbar, click More Materials and choose Local>Porous
Material .
2 In the Settings window for Porous Material, locate the Geometric Entity
Selection section. From the Selection list, choose Channel blocks.
Note: A description of how to set up these selections can be found in Geometry.

Fluid
3 Right-click Porous Material and choose Fluid . Notice that the generated
global material Gas: Nitrogen is predefined for this node.
4 Right-click Porous Material and choose Solid . From the Solid Properties
section, Material list, choose Solid: Monolith Material.
5 In the θs text field, type 1-por.
Add a material for the monolith walls by linking to the global monolith material.

58 |
Walls
1 In the Materials toolbar, click More Materials and choose Local>Material Link
.
2 In the Settings window for Material Link, locate the Geometric Entity Selection
section and choose Supporting walls from the Selection list.
3 Locate the Link Settings section and choose Solid: Monolith Material (mat 1)
from the Material list.
4 In the Label text field, type Walls.
Now it is time to set up the physics interfaces that describe the mass transport, heat
transfer, and fluid flow in the monolithic reactor. Before continuing though, in
the Model Builder toolbar, click Collapse All to get a better overview of the
tree for the remainder of the model setup.

Transport of Diluted Species in Porous Media Interface

During the Generate Space-Dependent Model procedure several feature nodes

were added along with the new physics interfaces. Now go through these features
one by one and enter settings, and make sure that they are assigned to the proper
domains and boundaries in the 3D reactor.
1 In the Model Builder window, under 3D Model, click
Transport of Diluted Species in Porous Media (tds) .
2 In the Settings window, under Domain Selection, choose Channel blocks from
the Selection list. This is the only domain where there is diffusion of diluted
species in porous media.
3 In the Model Builder window, expand the Transport of Diluted Species in
Porous Media (tds) node.

P OROUS M EDIUM
1 In the Model Builder window, expand the Porous
Medium 1 node, then click Fluid 1. The ‘D’ in
the upper left corner of a node denotes that it is a
default node.
2 In the Settings window, locate the Model Input
section. The Temperature is automatically set to
Temperature (ht). Click the Go to Source
button to see the Contributing Entities.
3 In the Settings window for Fluid 1, locate the Convection section.

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4 From the u list, choose Darcy’s velocity field (dl).
The mass transport model for the monolith channels assumes that there is only
diffusive mass transport in the axial direction of the reactor, here, along the x-axis.
This is modeled by specifying the diffusivity only in the first element of the
diagonal diffusion matrix. This is done in the following way:
5 Locate the Diffusion section. From the Source list, choose Material.
6 For each species, change from Isotropic to Diagonal for the Fluid diffusion
coefficient.
7 For each species, set all but the xx-component of the diffusion coefficients to
zero. Then enter the following expressions, one for each species, for the
xx-component (upper left corner of the matrix):
- For DF,cH2O type pp1mat1.df4.D11
- For DF,cNH3 type pp1mat1.df1.D11
- For DF,cNO type pp1mat1.df2.D11
- For DF,cO2 type pp1mat1.df3.D11
The entered expressions can be found
under Global Definitions>Materials>Gas:
Nitrogen (pp1mat1) node. D11
represents the xx-component in the
diffusivity matrix.
8 From the Effective diffusivity model
list, choose No correction.

60 |
The Diffusion section should now look like this:

This model is highly nonlinear due to the reaction kinetics. In this case, to solve
all the physics simultaneously, starting from a non-reacting system leads to a more
robust simulation. To achieve this set the initial concentrations to zero.

I NITIAL V ALUES 1
1 In the Model Builder window, under Transport of Diluted Species in Porous
Media, click Initial Values 1 .
2 In the Settings window for Initial Values, locate the Initial Values section and
change the default concentrations to zero.
In addition to the default feature nodes, the nodes Reactions 1, Inflow 1 and
Outflow 1 were also added during the Generate Space-Dependent Model
procedure. The Reaction feature gets input from the Chemistry interface in the
3D model. The inflow and outflow features’ icons are marked with the warning
sign in the Model Builder window. The warning message, seen when placing
the mouse pointer on top of the icons, reveals that they are empty and need to be
assigned to the proper domains and boundaries in the 3D reactor model.

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I NFLOW 1
1 In the Model Builder under Transport of Diluted Species in Porous Media, click
Inflow 1 .
2 In the Settings window under Boundary Selection, choose Inlet from the
Selection list.

O UTFLOW 1
1 In the Model Builder, click Outflow 1 .
2 In the Settings window under Boundary Selection, choose Outlet from the
Selection list.

Heat Tran sfer in Po rous Media

Next, set up the Heat Transfer in Porous Media interface. Similarly to the
procedure used for the mass transfer interface, go through the generated feature
nodes, modify and add as needed.

P OROUS M EDIUM
Begin by specifying the Fluid in the Porous Medium feature,
accounting for convective and conductive heat transfer in
the channel blocks.

Fluid
1 In the Model Builder window, under the Heat Transfer in Porous Media 1
interface, expand the default Porous Medium 1 node , then click Fluid 1 .
2 In the Settings window, locate the Heat Convection section and choose Darcy’s
velocity field (dl) from the u list.
3 Locate the Heat Conduction Fluid section. From the kf list, choose From
material.
4 Locate the Thermodynamics, Fluid section. Choose From material in the
corresponding list for each of these properties: ρf, Cp,f, and γ.

62 |
Note that the fluid properties are now defined by the corresponding node of the
Porous Material.

Porous Matrix
1 In the Model Builder window, click Porous Matrix 1.
2 In the Settings window for Porous Matrix 1, locate the Matrix Properties
section and choose Solid phase properties from the Define list.
3 In the Settings window, locate the Heat Conduction, Porous Matrix section and
choose User defined from the ks list. Additionally, choose Diagonal.
Specifying the diagonal thermal conductivity elements is needed to model
anisotropic conductive heat transfer in the channel blocks.
4 In the ks table, enter the following settings:

0.13[W/m/K] 0 0
0 0.25[W/m/K] 0
0 0 0.25[W/m/K]

Note that apart from the conductivity, the matrix properties are now defined by
the Solid node added to the Porous Material.

I NITIAL V ALUES
1 In the Model Builder window, click Initial Values 1, and locate the Initial Values
section in the Settings window. Type T_in in the T text field. This parameter
was previously defined in Parameters.

H EAT S OURCE
Associate the Heat Source to the exothermic chemistry within the channel blocks.
The Heat Source feature and the expressions describing the heat source are
generated by the Generate Space-Dependent Model feature, linking the 3D
model to the plug flow model.
1 Under Heat Transfer in Porous Media 1 (ht) , click the Heat Source 1 node
.
2 In the Settings window under Domain Selection, choose Channel blocks from
the Selection list.

T EMPERATURE
1 In the Model Builder window, click Temperature 1 and locate the Boundary
Selection section in the Settings window.
2 From the Selection list, choose Inlet walls.

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O UTFLOW
1 In the Model Builder window, click Outflow 1 and locate the Boundary
Selection section in the Settings window.
2 From the Selection list, choose Outlet.

S OLIDS
Now define the conductive heat transfer in the supporting solid walls. Note that
the physical properties of the walls are taken from the material Solid: Monolith
Material, associated with that domain. The association was performed in the
section Walls.
1 In the Model Builder click the Heat Transfer in Porous Media interface
node.
2 In the Physics toolbar, click Domains and choose Solid .

3 In the Settings window, locate the Domain Selection section and choose
Supporting walls from the Selection list.
Complete the set up of the Heat Transfer interface by assigning the heat flux,
symmetry and inflow boundary conditions.

H EAT F LUX 1
1 In the Physics toolbar, click Boundaries and
choose Heat Flux .
2 In the Settings window, locate the Boundary
Selection section and choose Reactor surface from
the Selection list.
3 Locate the Heat Flux section and click the
Convective heat flux button.
- In the Heat transfer coefficient (h) text field
type 10[W/(m^2*K)].
- In the External temperature (Text) text field type T_amb.

64 |
H EAT F LUX 2
1 In the Physics toolbar, click Boundaries and click to
add a second Heat Flux node .
2 In the Settings window:
- In the Boundary Selection section, choose
Outlet walls from the Selection list.
- In the Heat Flux section click the Convective
heat flux button. In the Heat transfer
coefficient (h) text field type 1. In the External
temperature (Text) text field type T_amb.

S YMMETRY
1 In the Physics toolbar, click Boundaries and choose Symmetry .
2 In the Settings window, locate the Boundary Selection and choose Symmetry
from the Selection list.

I NFLOW
1 In the Physics toolbar, click Boundaries and choose Inflow .
2 In the Settings window, locate the Upstream Properties section and type T_in
in the Tustr text field.
3 Locate the Boundary Selection section and choose Inlet from the Selection list.
The node sequence in the Model Builder under the Heat Transfer in Porous
Media interface should now match this figure:

D a r cy ’s La w I n t e r f a c e

Follow these steps to set up the Darcy’s Law interface that describes the fluid flow
through the reactor.
1 In the Model Builder window, under 3D Model (comp2), click the Darcy’s
Law 1 (dl) node .

| 65
2 In the Settings window, locate the Domain Selection and choose Channel
blocks from the Selection list.

F LUID AND M ATRIX P ROPERTIES 1

1 Expand the Darcy’s Law (dl) node and click Fluid and
Matrix Properties 1 .
2 Locate the Fluid Properties section and choose Gas:
Nitrogen (pp1mat1) from the Fluid material list.
3 From the Density ρ and Dynamic_viscosity μ lists choose From material.
4 Locate the Matrix Properties section and choose Solid: Monolith Material (mat
1) from the Porous material list.
5 From the Porosity εp list, choose User defined. In the associated text field, type
1-por.
6 From the Permeability κ list, choose User defined and Diagonal. In the κ table,
enter the following settings:

3.3e-7 0 0
0 0 0
0 0 0

S ETTING THE BOUNDARY CONDITIONS

Now specify the boundary conditions for the Inlet, Pressure, and Outlet features.
1 In the Model Builder window, click Inlet 1 .
2 Locate the Boundary Selection section and choose Inlet from the Selection list.
3 Locate the Boundary Condition section and choose Mass flow from the list.
4 In the Mass flow section, type M0_in in the M0 text field.
1 In the Model Builder window, click Outlet 1 .
2 Locate the Boundary Selection section and choose Outlet from the Selection
list.
3 Locate the Boundary Condition section and choose Pressure from the list.
Leave the default pressure value as zero.

66 |
This completes the setup of the model equations describing the reacting flow and
heat transfer in the monolith. The sequence of nodes for the 3D Model in the
Model Builder should match this figure.

Before solving the problem numerically, the geometry needs to be discretized with
a mesh.

Me sh

First create a Free Triangular mesh at the reactor inlet face and along two edges in
the Symmetry boundary. Then complete the mesh by sweeping in the axial
direction of the reactor.

F REE T RIANGULAR
1 In the Mesh toolbar from the Boundary menu, choose Free Triangular .
2 In the Settings window for Free Triangular, locate the Boundary Selection
section and choose Inlet end from the Selection list.

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Size 1
1 Right-click Free Triangular 1 and choose Size .
2 In the Settings window for Size, locate the Geometric Entity Selection section
and choose Inlet walls from the Selection list.
3 Click the Custom button in the Element Size section.
4 Locate the Element Size Parameters section, select the
Maximum element size check box and type 2.2 in the
associated text field.
5 Select the Resolution of narrow regions check box and
type 0.85 in the associated text field.
6 Click Build All .
Now add a second Size feature to improve the mesh
along two of the edges in the Symmetry boundary.

Size 2
1 In the Model Builder window, right-click Free Triangular 1 and choose Size
.
2 In the Settings window for Size, locate the Geometric Entity Selection section
and choose Edge from the Selection list.
3 Select Edges 5 and 17 only.
4 Locate the Element Size section and click the Custom button.
5 Locate the Element Size Parameters section, select the Maximum element size
check box and type 5 in the associated text field.
6 Click Build All .
Now complete the mesh using the Swept feature.

S WEPT
1 In the Model Builder window, right-click Mesh 1 and choose Swept .
2 Right-click Swept 1 and choose Distribution .
3 In the Settings window, locate the Distribution section and
type 50 in the Number of elements text field.

68 |
4 Click Build All , then click the Zoom Extents button in the Graphics
toolbar to view the entire geometry.

Study 2

It is time to solve the 3D model. Note that the Reaction Engineering interface
should not be computed for the space-dependent model, it can only be solved for
the 0D case. Therefore, keep the default study settings for Study 1.
1 In the Model Builder window, click Study 2 .
2 In the Settings window, locate the Study Settings section and clear the Generate
default plots check box.
3 In the Home toolbar, click Compute .

| 69
Results — 3D Model

Follow these steps to create Figure 9, Figure 10, and Figure 11 for the 3D monolith
model.

C ONVERSION 3D M ODEL - F IGURE 9

1 In the Home toolbar, click Add Plot Group and choose 3D Plot Group .
2 In the Settings window, type Conversion 3D Model in the Label text field.
3 Locate the Color Legend section and choose Left from the Position list.
4 Right-click the Conversion 3D Model node and choose Isosurface .
5 In settings window locate the Expression section and type (F_NO_in/
vrate-cNO)/(F_NO_in/vrate) in the Expression text field. This plots the
conversion of NO in the reactor.

6 Locate the Levels section and type 20 in the Total levels text field.
7 In the Graphics toolbar, click the Zoom Extents button.
8 In the Conversion 3D Model toolbar, click Plot .
The plot in Figure 9 is now displayed in the Graphics window.

T EMPERATURE 3D M ODEL - F IGURE 10

1 In the Home toolbar, click Add Plot Group and choose 3D Plot
Group .
2 In the Settings window, type Temperature 3D Model in the Label text field.
3 Locate the Color Legend section and choose Left from the Position list.
4 Right-click the Temperature 3D Model node and choose Slice .
5 Locate the Expression section and type T in the Expression text field.
6 Locate the Plane Data section and type 10 in the Planes text field.
7 In the Graphics toolbar, click the Zoom Extents button.
8 In the Temperature 3D Model toolbar, click the Plot button .
The plot in Figure 10 is displayed in the Graphics window.

70 |
M ONOLITH VIEW - F IGURE 11
In the last plot for this tutorial example, the full
monolith structure is visualized (see Figure 11). This
is accomplished by creating Sector 3D datasets, Slice
plots, and using Filter.
In the first step, create the dataset for the selectivity
data.

Sector 3D datasets
1 In the Results toolbar, click More Datasets
and choose Sector 3D .
2 In the Settings window, type Monolith in the
Label text field.
3 Locate the Axis Data section and in row Point 2
set
- X to 1
- Z to 0
4 Locate the Symmetry section and type 8 in the
Number of sectors text field.
5 From the Sectors to include list, choose Manual.
6 From the Transformation list, choose Rotation
and reflection.
7 Find the Radial direction of reflection plane
subsection and type
- 0 in the X text field and
- 1 in the Z text field.
8 Click to expand the Advanced section and select the Define variables check box.
This setting is needed later by the Filter feature, used to exclude one sector from
the Selectivity dataset.
9 Click Plot in the Settings window to see the geometry of the created dataset.
In the next step, create the dataset that the temperature data will be added to. This
is done by creating a Sector 3D dataset with only two sectors.
1 Right-click Monolith and choose Duplicate .
2 In the Settings window, type Temperature sector in the Label text field.
3 Locate the Symmetry section and type 2 in the Start sector text field.
4 Type 1 in the Number of sectors to include text field.

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Now create a plot group that will use the created datasets.

3D Plot Group
1 In the Results toolbar, click 3D Plot Group .
2 In the Settings window, type Monolith view in the Label text field.
3 Locate the Data section and choose Monolith from the Dataset list.
4 Locate the Plot Settings section and clear the Plot dataset edges check box.
5 Select the Show units check box in the Color Legend section.
Now add plots to the created plot group. The plots will use the sector 3D datasets.
Begin with the selectivity data.

Slice Plot Selectivity

1 Right-click Monolith view and choose Slice .
2 In the Settings window for Slice, type Selectivity in the Label text field.
3 Locate the Expression section. In the Expression text field, type S.
4 Select the Description check box.
5 Locate the Plane Data section and choose Coordinates from the Entry method
list.
6 Click Range and choose Number of values from the Entry method list in
the Range dialog box.
7 In the Start text field, type 0 and in the Stop text field type L (the parameter for
reactor length).
8 In the Number of values text field, type 5. Click Replace.
9 In the Monolith view toolbar, click Plot .
Now add the plot for the temperature data.

Slice Plot Temperature

1 Right-click Selectivity and choose Duplicate .
2 In the Settings window, type Temperature in the Label text field.
3 Locate the Data section and choose Temperature sector from the Dataset list.
4 Locate the Expression section and type T in the Expression text field.
5 In the Description text field, type Temperature.
6 Locate the Coloring and Style section and choose HeatCameraLight from the
Color table list.

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By looking at the plot in the Graphics window we notice that the selectivity data
is plotted on top of the temperature data. Use Filter to exclude the selectivity data
from the temperature sector.

Filter
1 In the Model Builder window, click Selectivity.
2 In the Settings window, click to expand the Quality section and choose None
from the Smoothing list.
3 Right-click Selectivity and choose Filter .
4 In the Settings window, locate the Element Selection section and type
sec1number!=2 in the Logical expression for inclusion text field.
5 In the Monolith view toolbar, click Plot .
The plot in Figure 11 contains an arrow surface displaying the Darcy’s velocity
field. Create that plot using a Cut Plane dataset and an Arrow Surface plot.

Cut Plane
1 In the Results toolbar, click Cut Plane . This adds a Cut Plane dataset.
2 In the Settings window, locate the Data section and choose Monolith from the
Dataset list.
3 Locate the Plane Data section and choose YX-planes from the Plane list.
4 In the Z-coordinate text field, type 2. Click Plot .
5 In the Model Builder window, right-click Monolith view and choose Arrow
Surface .
6 In the Settings window for Arrow Surface, locate the Data section and choose
Cut Plane 1 from the list.
7 Click Replace Expression in the upper -right corner of the Expression
section. From the Menu, choose 3D Model (comp2)>Darcy’s Law 1>Velocity
and pressure>dl.u,dl.v,dl.w -Darcy’s velocity field.
8 Locate the Coloring and Style section and choose Cone from the Arrow type
list. Select the Scale factor check box and type 80 in the corresponding text field.
9 In the Monolith view toolbar, click Plot .
10Click the Go to Default View button in the Graphics toolbar.
The final step is to derive values for the outlet average conversion, as well as the
highest temperature reached in the reactor.

Average Conversion and Maximum Temperature

1 In the Results toolbar, click More Derived Values and choose
Average>Surface Average .

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2 In the Settings window, locate the Selection section and choose Outlet from the
Selection list.
3 Locate the Expression section. Click Clear Table .
4 In the table, enter the following settings:

EXPRESSION UNIT DESCRIPTION

(F_NO_in/vrate-chem.c_NO)/(F_NO_in/vrate) 1 Conversion

5 Click Evaluate .
6 In the Results toolbar, click More Derived Values and choose
Maximum>Volume Maximum .
7 In the Settings window, locate the Selection section and choose All domains
from the Selection list.
8 Click Evaluate .

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