The Reaction Engineering Interface
The Reaction Engineering (re) interface (), found under the Chemical Species Transport branch () when adding a physics interface, is used to model several chemical reactor types and the evolution of chemical reactions over time. The mass balance and energy balance equations describing these systems assume perfect or well-defined mixing in the reactor. Essentially, the physics interface simulates, tank, and plug flow chemical reactors to investigate the behavior over time of a chemical reaction.
The reaction kinetics expressions of a reactor can be exported to a space-dependent model, using the Generate Space-Dependent Model feature. This gives you the power to simulate reacting systems as they depend on fluid flow, mass transfer, and heat transfer — in other words, including space dependencies.
Add physics features from the toolbar, or right-click Reaction Engineering to select features from the context menu. Many of the fields and nodes described in this section are made available when either a Reaction or a Species (or both) subnode is added to the Model Builder. Because nodes and subnodes are accessible at any time, and any change is updated throughout the model, reactions and species are often defined before the settings described in this section.
All predefined constants and expressions can be overwritten by user-defined expressions. This makes it possible to go beyond the modeling assumptions that are the defaults in this physics interface.
The following is a description of the features and fields available on the Settings window for Reaction Engineering.
Settings
The Label is the default physics interface name.
The Name is used primarily as a scope prefix for variables defined by the physics interface. Refer to such physics interface variables in expressions using the pattern <name>.<variable_name>. In order to distinguish between variables belonging to different physics interfaces, the name string must be unique. Only letters, numbers, and underscores (_) are permitted in the Name field. The first character must be a letter.
The default Name (for the first physics interface in the model setup) is re.
Equation
This section displays the governing equations according to the selection of reactor types in the Reactor section.
Reactor
Select a Reactor type to define the reaction system. The available reactor types are: Batch, Batch, constant volume, CSTR, constant volume, CSTR, constant mass/generic, Semibatch, and Plug flow. Each reactor type solves a mass balance based on properties typical to the type, such as reactor volume, volumetric production, or flow rate:
Batch: In reactors no mass enters or leaves the system. This type can account for a variable reactor volume.
Batch, Constant Volume: Same as Batch but where the reactor volume is assumed to be constant. As this is the situation for most reacting systems, this is the default condition.
CSTR, Constant Mass/Generic: Continuous stirred tank reactors (CSTR) differ from batch reactors, since these allow species to enter and leave the reactor by means of feed inlet streams and outlet streams. The system’s volume is allowed to change, such as in a car engine cylinder or a balloon. This reactor model can be solved either for a constant mass condition or by selecting a specific outlet flow.
CSTR, Constant Volume: Same as the CSTR with constant mass/generic reactor but assumes that the volume is constant during operation.
Semibatch: Semibatch reactors differ from batch reactors in that they allow reactants to enter the reactor by means of one or several feed inlet streams.
Plug Flow: In the plug flow reactor, the species concentrations and the temperature vary with position. Plug flow in a tubular configuration means that concentration and temperature gradients develop only in the axial direction, but not in the radial direction.
For each Reactor type, additional settings are shown in Table 2-1. If a surface reaction or species is included, except for the Plug flow reactor type, the surface reaction area is also a parameter. The parameters and expressions are used in the mass balance equations.
Volumetric production rate vp and Volumetric outlet rate v
Volumetric production rate vp and Reactor volume Vr
Volumetric Rate
For CSTR, constant volume and Semibatch reactor types, the Volumetric production rate (vp) is available. For Automatic, the in-built Volumetric production rate expression is shown. If User defined is selected, the expression can be changed (SI unit: m3/s). For instance, this enables the setting of zero (0) volumetric production rate, which ignores volume changes due to reactions.
For liquid phase reactions, the Automatic expression for the Volumetric production rate varies with the reaction rate of each species as defined by:
(2-76)
The physics interface automatically inserts the stoichiometric coefficients (νij) and reaction rate expressions for each species (Ri) that depend on j number of reactions of a rate (rj), as defined in the Reaction feature node. Furthermore, the values of the molar mass (Mi) and the species density (ρi) are automatically taken from the Species features.
For gas phase reactions, the Automatic expression for the Volumetric production rate is similarly given by:
(2-77)
For CSTR, constant mass/generic, select Volumetric rate to either Constant mass (Automatic) or Generic. The Constant mass (Automatic) selection shows both the expression for Volumetric production rate (vp) (Equation 2-77 for gas, or Equation 2-76 for liquid phase reactions) and Volumetric outlet rate (v) (Equation 2-78). The latter is derived from constant mass flow condition through the reactor:
(2-78)
The mixture density (ρf) of m number of feed inlet streams is determined in the same way as in the Mixture Properties section. For Generic both the Volumetric rate properties can be edited (SI unit: m3/s). This means that it is possible to completely control the volumetric outlet rate from the CSTR.
For the Plug flow reactor, the Volumetric flow rate along the reactor is set. The Automatic definition computes a variable volumetric flow rate that depends on the molar flow rate of each species (Fi).
(2-79)
(2-80).
The default value for p (Reactor pressure) is 1 atm in Equation 2-81 and it is set in the Mixture Properties section.
Reactor Volume
This input field sets the Reactor volume Vr — that is, the fluid volume in which chemical reaction takes place. The Batch reactor type can account for a changing volume, thus a time-dependent volume expression can be entered here.
Surface Reaction Area
Once a surface reaction, or a surface species, has been added, for all reactor types except Plug flow, the Surface reaction area settings become visible. Here, the area of the surface on which the surface reactions take place can be defined. The surface area can either be defined directly as a parameter, or by defining the Surface area to volume ratio.
Energy Balance
From the list select to Exclude or Include the energy balance, which in essence determines whether the system is solved for either isothermal or nonisothermal conditions, respectively. The latter introduces the temperature as a variable in the interface.
If Exclude is chosen, enter a Temperature T for the system.
It is possible to incorporate cooling or heating of the reactor. This is done in External heating or cooling (Qext). Enter a negative value to account for cooling or a positive one for heating (SI unit: W). Note that for the Plug Flow reactor type, the External heating or cooling (Q) is defined per reactor volume (SI unit: W/m3).
Mixture Properties
Thermodynamics
All property parameters and property functions required by the interface can be automatically created by coupling to a system added to the Thermodynamics node. To do so click the Thermodynamics check box and select an existing Thermodynamic System.
The Thermodynamics check box is enabled except if:
the Thermodynamics node, including one or more systems, is not added under Global Definitions, or
no species are added in the Reaction Engineering interface, or
a CHEMKIN file is imported in the Reaction Engineering interface.
Phase
Use the Phase list to specify the state of aggregation of the mixture.
Density
This setting is available when the Calculate mixture properties check box in the Calculate Transport Properties section has been selected.
Two settings are always available for the mixture Density: Automatic or User defined. The Thermodynamics options is available when the interface is coupled to a Thermodynamic System, and all interface species has been matched to species in the system. In this case the density is defined by a function automatically added under the thermodynamic system coupled to.
The mixture density is transferred to physics interfaces set up by the Generate Space-Dependent Model feature. The density is compiled for both multicomponent and solute-solvent solutions.
The Automatic setting uses the following logic:
Automatic selected for Liquid, considers the liquid as ideal and incompressible. The liquid mixture density depends on the density of i number of pure species (ρi) and the species mass fraction (wi).
The mass fraction is given by the species concentration (ci) and the molar mass (Mi).
Automatic set for Gas calculates the gas mixture density (ρ) from the concentrations (ci) and molar masses (Mi) of the mixture species, which are automatically taken from Species features.
(2-81)
If a Species Type is set to Solvent and the Mixture is Liquid, the mixture density is the same as the solvent density as defined in Density in General parameters in the Species node. When Mixture is Gas, the mixture density is calculated from Equation 2-81 only for the species set as Solvent.
Reactor Pressure
The Phase - Gas setting displays the Reactor pressure. For all reactor types, except the Plug flow reactor, select either a pressure computed from the Ideal gas law or from any other expression using the User defined option. The Batch and Semibatch reactor types also have the option to keep the reactor pressure Constant during reaction.
For the Plug Flow reactor, the Reactor pressure can be entered in the case of the Reactor section having the Volumetric rate set to Automatic, in which case the User defined alternative is available and a constant pressure fits the conditions.
When the Thermodynamics check box is selected in the Mixture Properties section and the species are fully coupled (see the section below), the reactor pressure is set to Thermodynamics indicating that it is automatically computed.
Species Matching
The Species Matching section is activated when the Thermodynamics check box is selected in the Mixture Properties section. The species in the Reaction Engineering interface can be matched to species in the Thermodynamic System. This ensures that the arguments in the thermodynamic system functions are correctly defined.
Use the drop-down lists in the From Thermodynamics column to match each species in the interface to a species in the coupled thermodynamic system.
For each species matched, the required property parameters and functions are added under to the corresponding thermodynamic system.
When all species are matched, the interface is considered fully coupled and functions representing mixture properties, such as density, are also added automatically under the corresponding thermodynamic system.
Calculate Transport Properties
Transport properties are not utilized in the reactor equations available in the Reaction Engineering interface, where perfect mixing is assumed. However, transport properties such as diffusivity, thermal conductivity, and viscosity are of central importance when solving time- and space-dependent models. The physics interface helps to set up detailed expressions of species transport properties and transfers them automatically to the multiphysics model through the Generate Space-Dependent Model feature.
The most general description of a mixture is the one that treats the mixture as a multicomponent solution, where all species interact with each other. A simplified description, but still a common one, assumes that the solution has a solvent that dominates the properties of the solution. The solutes in such a solution interact only with solvent molecules.
Select the Calculate mixture properties check box to enable calculation of mixture transport properties exported from the Reaction Engineering interface.
From the list for each property, select the in-built Automatic expression or set a User defined entry. The mixture properties you can transfer for space-dependent models are:
Heat capacity (cp) (SI unit: J/(kg·K)) (this is available when the Energy Balance is set to Include)
Thermal conductivity (k) (SI unit: W/(m·K))
Dynamic viscosity (μ) (SI unit: Pa·s) (this is available when a Species Type is set to Solvent)
Mixture density (ρ) (SI unit: kg/m3) (this is available in the Mixture Properties section)
All species properties needed to compute the mixture properties are entered in the Species Transport Expression or Species Thermodynamic Expression in the Species node.
Equilibrium Species Vector
This section is available when at least one equilibrium reaction has been defined, that is, when a Reaction node incorporates at least one Equilibrium reaction (Reaction type is set to Equilibrium), or when at least one equilibrium reaction has been defined in an Equilibrium Reaction Group.
In the Predefined dependent species (separated by ‘,’) text field, edit, if necessary, the species that depends on the composition of the other species according to the Equilibrium expression in the Reaction node. To minimize the impact of any numerical errors, it is recommended to set the species with the highest concentration as dependent species. The default species is set to the leftmost species in the Reaction formula.
The Suppress negative concentrations check-box exists to aid the computation of equilibrium reaction systems. A selected check-box ensures that no negative values of concentrations are accepted as solution to the equilibrium condition.
Activity
Select the Use activity check box to solve for species activities instead of species concentrations, which is a common approach when non-ideal fluids are modeled.
An activity coefficient other than 1 can be set for each species for the Species node in the Species Concentration/Activity section.
CHEMKIN Import for Species Properties
This section enables CHEMKIN® import to simulate complex chemical reactions in gas phase.
Two types of CHEMKIN input files can be imported here — Thermo and Transport, for thermodynamic properties and transport properties respectively. Properties for either volumetric or surface species are supported. Click Browse to locate the CHEMKIN file to be imported, then click Import. For Thermo the imported data is directly entered in the NASA format fields in the Species Thermodynamic Expressions section. For Transport the imported data is entered in the Species Transport Expressions section.
Advanced Settings
To display this section, click the Show More Options button () and select Advanced Physics Options.
The Uniform scaling of concentration variables check box is not selected by default. When selected, all concentration variables are scaled using the same scale factor in the Study node. Enabling uniform scaling can decrease solver time for problems involving many concentration variables.