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Nonisothermal Plug Flow Reactor

Introduction
This model considers the thermal cracking of acetone, which is a key step in the
production of acetic anhydride. The gas phase reaction takes place under
nonisothermal conditions in a plug flow reactor. As the cracking chemistry is
endothermic, control over the temperature in the reactor is essential in order to achieve
reasonable conversion. When the reactor is run under adiabatic conditions, the model
shows how the conversion of acetone can be affected by mixing the reactant with inert.
Furthermore, it is illustrated how to affect the conversion of acetone by means of a heat
exchanger supplying energy to the system.

The example details the use of the predefined plug flow reactor type in the Chemical
Reaction Engineering Module and how to set up and solve models describing
nonisothermal reactor conditions. You will learn how to model adiabatic reactor
conditions as well as how to introduce heat exchange.

Model Definition
This model is related to an example found in Ref. 1. An essential step in the gas-phase
production of acetic anhydride is the cracking of acetone (A) into ketene (K) and
methane (M):

CH3COCH3 CH2CO + CH4 (1)

(A) (K) (M)

The rate of reaction is

r1 = k1 cA (2)

where the rate constant is given by the Arrhenius expression

E1
k 1 = A 1 exp ----------- (3)
R g T

For the decomposition of acetone described above, the frequency factor is

A1 = 8.21014 (1/s), and the activation energy is E1 = 284.5 (kJ/mol).

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Chemical reaction takes place under nonisothermal conditions in a plug flow reactor,
illustrated schematically in Figure 1.

Figure 1: The Plug flow reactor is a predefined reactor type in the Chemical Reaction
Engineering Module.

Species mass balances are described by:

dF
---------i = R i (4)
dV

where Fi is the species molar flow rate (mol/s), V is the reactor volume (m3), and Ri
is the species rate expression (mol/(m3s)). Concentrations needed to evaluate rate
expressions are found from:

Fi
c i = ----- (5)
v

where v is the volumetric flow rate (m3/s). By default, the Reaction Engineering
interface treats gas phase reacting mixtures as being ideal. Under this assumption the
volumetric flow rate is given by:

Rg T
v = Fi ----------
p
- (6)
i

where p is the pressure (Pa), Rg denotes the ideal gas constant (8.314 J/(molK)), and
T is the temperature (K).

The reactor energy balance is given by:

dT
Fi Cp, i -------
dV
- = w s + Q + Q ext (7)
i

In Equation 7, Cp,i represents the species molar heat capacity (J/(molK)), ws is the
shaft work per unit volume (J/(m3s)), and Q denotes the heat due to chemical
reaction (J/(m3s)):

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Q = Hj rj (8)
j

where Hj is the heat produced by reaction j. The term Qext represents external heat
added or removed from the reactor. The present model treats both adiabatic reactor
conditions:

Q ext = 0

and the situation where the reactor is equipped with a heat exchanger jacket. In the
latter case Qext is given by:

Q ext = Ua ( T amb T ) (9)

where U is the overall heat transfer coefficient (J/(m2sK)), a is the effective heat
transfer area per unit of reactor volume (1/m), and Tamb is the temperature of the heat
exchanger medium (K). The Reaction Engineering interface automatically sets up and
solves Equation 4 and Equation 7 as the predefined Plug flow reactor type is selected.
As input to the balance equations you need to supply the chemical reaction formula,
the Arrhenius parameters, the species thermodynamic properties, as well as the inlet
molar feed of reactants.

Following the step-by-step instructions below, you will first model the cracking of
acetone in an adiabatic plug flow reactor. See how the acetone conversion varies with
the ratio of reactant to inert in the inlet stream. In second model, add the effects of a
heat exchanger jacket and observe how the added energy drives the reaction to
completion.

Working with Thermodynamic Polynomials

The Reaction Engineering interface uses the following set of polynomials as default
expressions describing species thermodynamic properties:

2 3 4
C p, i = R g ( a 1 + a 2 T + a 3 T + a 4 T + a 5 T ) (10)

a2 2 a3 3 a4 4 a5 5
h i = R g a 1 T + ------ T + ------ T + ------ T + ------ T + a 6 (11)
2 3 4 5

a3 2 a4 3 a5 4
s i = R g a 1 ln T + a 2 T + ------ T + ------ T + ------ T + a 7 (12)
2 3 4

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Here, Cp,i denotes the species heat capacity (J/(molK)), T the temperature (K), and
Rg the ideal gas constant, 8.314 (J/(molK)). Further, hi is the species molar enthalpy
(J/mol), and si represents its molar entropy (J/(molK)). A set of seven coefficients
per species are taken as input for the polynomials above. The coefficients a1 through
a5 relate to the species heat capacity, the coefficient a6 is associated with the species
enthalpy of formation (at 0 K), and the coefficient a7 comes from the species entropy
of formation (at 0 K).

The format outlined by Equation 10 through Equation 12 is referred to as

CHEMKIN or NASA format (Ref. 2). This is a well established format, and database
resources list the needed coefficients for different temperature intervals. Many web
based data resources exist for CHEMKIN thermodynamic data and otherwise (Ref. 3).
It is therefore often a straight forward task to assemble the thermodynamic data
required and then import it into your reaction model.

CREATING A THERMODYNAMIC DATA FILE

CHEMKIN thermodynamic files typically contain blocks of data, one block for each
species. Such a data block is illustrated in Figure 2 for gas phase acetone.

Figure 2: Thermodynamic data block on the CHEMKIN format.

The first line starts with the species label, given with a maximum of 18 characters,
followed by a 6 character comment space. Then follows a listing of the type and
number of atoms that constitute the species. The G comments that this is gas phase
data. The line ends with listing of three temperatures, defining two temperature
intervals. Lines 2 through 4 contain two sets of the polynomial coefficients, a1
through a7. The first set of coefficients is valid for the upper temperature interval, and
the second for the lower interval.

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A complete CHEMKIN thermodynamics file has the structure illustrated in Figure 3.

Figure 3: Thermodynamic data file on the CHEMKIN format.

The keyword thermo always starts the text file. The subsequent line lists three
temperatures, defining two temperature intervals. These intervals are used if no
intervals are provided in the species specific data. Then follows the species data blocks,
in any order. The keyword end is the last entry in the file.

The data file reproduced in Figure 3 is used in the present model. It was constructed
by creating a text-file with species data blocks from the Sandia National Labs
Thermodynamics resource (Ref. 4).

USING SUBSETS OF THERMODYNAMIC COEFFICIENTS

In some instances, not all coefficients a1 through a7 are available. Coefficients may also
be on a format differing from the NASA or CHEMKIN style. Input parameters can
still be put on the form of Equation 10 to Equation 12, as illustrated below.

For species A, K, M, and N2, Ref. 1 lists polynomials for the heat capacity on the form:

2
C p, i = a 1' + a 2'T + a 3'T (13)

Furthermore, the species enthalpies of formation at Tref = 298 K are provided:

SPECIES a1' a2' a3' h(298)

A 26.63 0.183 -45.86e-6 -216.67e3
K 20.04 0.0945 -30.95e-6 -61.09e3

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SPECIES a1' a2' a3' h(298)

M 13.39 0.077 -18.71e-6 -71.84e3
N2 6.25 8.78e-3 -2.1e-8 0

The data in the table above can be correlated with the polynomials given by
Equation 10 and Equation 11 by noting the relations:

a n'
a n = ------- n = 1, , 5 (14)
Rg

h ( T ref ) a2 2 a3 3
a 6 = ------------------- a 1 T ref + ------ T ref + ------ T ref (15)
Rg 2 3

Using Equation 14 and Equation 15, you find the coefficients to enter in the Reaction
Engineering interface.

SPECIES a1 a2 a3 a6
A 3.20 2.20e-2 -5.52e-6 -2.79e4
K 2.41 1.14e-2 -3.72e-6 -8.54e3
M 1.61 9.26e-3 -2.25e-6 -9.87e3
N2 0.752 1.06e-3 -2.53e-9 -2.71e2

Read more about how to work with thermodynamic data in the section Working with
Predefined Expressions in the Chemical Reaction Engineering Module Users Guide.

Results and Discussion

In a first model, the plug flow reactor is run under adiabatic conditions. The reactor is
fed with a total molar flow of 38.3 mol/s. Figure 4 shows the reactor temperature as
a function of the reactor volume for the case when only acetone enters the reactor. The

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reactor temperature decreases along the reactor length due to the endothermic
cracking reaction.

Figure 4: The reactor temperature (K) as a function of reactor volume (m3).

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Figure 5 shows the conversion of acetone. When pure acetone enters the reactor
conversion is no more than 30% at the reactor outlet

Figure 5: The conversion of acetone (%) as a function of reactor volume (m3).

Figure 6 shows the temperature profile of the plug flow reactor as a heat exchanger
supplies energy to the reacting system. Initially the energy consumption of the cracking
reaction is dominant, and the temperature in the system drops. As the reaction rate
drops off, the heat exchanger starts to heat up the system. The heating rate decreases

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with the temperature difference between the heat exchanger medium and reacting
fluid.

Figure 6: Temperature (K) as a function of volume (m3), for a reactor equipped with a
heat exchanger jacket.

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Figure 7 shows the conversion of acetone along with the reaction rate. Note how the
heat exchanger allows for relatively high reaction rates while maintaining high
conversion.

Figure 7: The conversion of acetone (%) and reaction rate (mol/(m3s)) as a function of
reactor volume (m3).

In this model, the effect of mixing the reactant acetone with inert nitrogen can be
studied by changing the parameter Afrac, describing the molar fraction of acetone at
the inlet.

References
1. H.S. Fogler, Elements of Chemical Reaction Engineering 3rd Ed., Prentice Hall
PTR, example 8-7, pp. 462468, 1999.

2. S. Gordon and B.J. McBride, Computer Program for Calculation of Complex

Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected
Shocks, and Chapman-Jouquet Detonations, NASA-SP-273, 1971.

3. See, for example, http://www.comsol.com/reaction

4. http://www.ca.sandia.gov/HiTempThermo/index.html

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Model Library path: Chemical_Reaction_Engineering_Module/

Tubular_Reactors/nonisothermal_plug_flow

Modeling Instructions

MODEL WIZARD
1 Go to the Model Wizard window.
2 Click the 0D button.
3 Click Next.
4 In the Add physics tree, select Chemical Species Transport>Reaction Engineering (re).
5 Click Next.
6 Find the Studies subsection. In the tree, select Preset Studies>Stationary Plug Flow.
7 Click Finish.

REACTION ENGINEERING
1 In the Model Builder window, under Model 1 click Reaction Engineering.
2 In the Reaction Engineering settings window, locate the Reactor Settings section.
3 From the Reactor type list, choose Plug flow.
4 Select the Calculate thermodynamic properties check box.
5 Locate the General section. In the p edit field, type 162e3.

Reaction 1
1 Right-click Model 1>Reaction Engineering and choose Reaction.
2 In the Reaction settings window, locate the Reaction Formula section.
3 In the Formula edit field, type A=>K+M.
4 Locate the Rate Constants section. Select the Use Arrhenius expressions check box.
5 In the Af edit field, type 8.2e14.
6 In the Ef edit field, type 284.5e3.

Species: A
1 In the Model Builder window, under Model 1>Reaction Engineering click Species: A.
2 In the Species settings window, click to expand the Species Feed Stream section.

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3 In the F0 edit field, type 38.3*A_frac.

Species 1
1 In the Model Builder window, right-click Reaction Engineering and choose Species.
2 In the Species settings window, locate the Species Formula section.
3 In the edit field, type N2.
4 Click to expand the Species Feed Stream section. In the F0 edit field, type
38.3*(1-A_frac).

Energy Balance
1 Right-click Reaction Engineering and choose Energy Balance.
2 In the Energy Balance settings window, locate the Energy Balance section.
3 In the T0 edit field, type 1035.
4 In the Model Builder window, click Reaction Engineering.
5 In the Reaction Engineering settings window, click to expand the CHEMKIN section.
6 Click the Browse button.
7 Browse to the models Model Library folder and double-click the file
nonisothermal_plug_flow_thermo.txt.

8 Click the Import button.

GLOBAL DEFINITIONS

Parameters
1 In the Model Builder window, right-click Global Definitions and choose Parameters.
2 In the Parameters settings window, locate the Parameters section.
3 In the table, enter the following settings:

Name Expression Description

Ua 16500[J/(m^3*s*K)] Heat transfer parameter
T_x 1150[K] Temperature, heat exchanger
medium
A_frac 1 Inlet mole fraction of A

DEFINITIONS

Variables 1
1 In the Model Builder window, under Model 1 right-click Definitions and choose
Variables.

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2 In the Variables settings window, locate the Variables section.

3 In the table, enter the following settings:

Name Expression Description

X_A (re.F0_A-re.F_A)/ Conversion, A
re.F0_A*100

STUDY 1

Step 1: Stationary Plug Flow

1 In the Model Builder window, expand the Study 1 node, then click Step 1: Stationary
Plug Flow.
2 In the Stationary Plug Flow settings window, locate the Study Settings section.
3 In the Volumes edit field, type range(0,0.5,20).
4 Select the Relative tolerance check box.
5 In the associated edit field, type 1.0E-4.
6 In the Model Builder window, right-click Study 1 and choose Show Default Solver.
7 Expand the Study 1>Solver Configurations node.

Solver 1
1 In the Model Builder window, expand the Study 1>Solver Configurations>Solver 1
node, then click Plug Flow Solver 1.
2 In the Plug Flow Solver settings window, click to expand the Absolute Tolerance
section.
3 In the Tolerance edit field, type 1.0E-5.
4 In the Model Builder window, right-click Study 1 and choose Compute.

RESULTS

Flow Rate (re)

1 In the Model Builder window, expand the Results>Flow Rate (re) node, then click
Global 1.
2 In the Global settings window, click Replace Expression in the upper-right corner of
the y-Axis Data section. From the menu, choose Definitions>Conversion, A
(mod1.X_A).
3 Click the Plot button.

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Temperature (re)
In the Model Builder window, under Results right-click Temperature (re) and choose
Plot.

REACTION ENGINEERING

Energy Balance
1 In the Model Builder window, under Model 1>Reaction Engineering click Energy
Balance.
2 In the Energy Balance settings window, locate the Energy Balance section.
3 In the Qext edit field, type Ua*(T_x-T).

STUDY 1
In the Model Builder window, right-click Study 1 and choose Compute.

RESULTS

Flow Rate (re)

1 In the Global settings window, click Add Expression in the upper-right corner of the
y-Axis Data section. From the menu, choose Reaction Engineering>Reaction
1>Reaction rate (mod1.re.r_1).
2 Click the Plot button.

Temperature (re)
In the Model Builder window, under Results right-click Temperature (re) and choose
Plot.

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